Immobilized Lewis Acid catalysts

ABSTRACT

Immobilized Lewis Acid catalyst comprising polymer having at least one Lewis Acid immobilized within the structure therein, said polymer having monomer units represented by the structural formula: 
     
         --[A].sub.a --[B].sub.b --[C].sub.c -- 
    
     wherein 
     a represents about 1 to about 99 mole % 
     b represents about 0 to about 50 mole % 
     c represents about 1 to about 99 mole % 
     a+b+c is preferably about 100%; ##STR1## C is selected from the group consisting of: ##STR2## (III) combinations thereof, wherein D is OH, halide, OR 4 , NH 2 , NHR 3 , OM&#39;, or OM&#34;; 
     E is the residue of the reaction of at least one Lewis Acid with the D substituent of monomer unit B; 
     R 1  represents proton, C 1  -C 24  alkyl group, or C 3  -C 24  cycloalkyl; 
     R 2  represents C 1  -C 24  alkylene group, C 3  -C 24  cycloalkylene, C 6  -C 18  arylene, or C 7  -C 30  alkylarylene; 
     R 3  represents C 1  -C 24  alkyl, C 3  -C 24  cycloalkyl, C 1  -C 24  aryl, or C 7  -C 30  alkylaryl; 
     R 4  represents C 1  -C 24  alkyl, C 3  -C 24  cycloalkyl, C 1  -C 24  aryl, or C 7  -C 30  alkylaryl; 
     M&#39; represents alkali metal; 
     M&#34; represents alkaline-earth metal. 
     Also disclosed are polymerization and alkylation processes utilizing the immobilized Lewis Acid catalysts. Another aspect of the present invention is a method of manufacturing immobilized Lewis Acid catalysts.

This is a division, of application Ser. No. 905,582, filed Jun. 26, 1992now U.S. Pat. No. 5,909,873, which is a continuation-in-part of U.S.Ser. No. 723,130 filed Jun. 28, 1991 now U.S. Pat. No. 5,288,677.

TECHNICAL FIELD

The field of art to which this invention pertains is catalysts, inparticular, immobilized Lewis Acid catalysts, and a process to preparepolymer using said catalysts as well as the polymer product.

BACKGROUND OF THE INVENTION

Lewis Acids have been widely used as catalysts in carbocationicpolymerization processes to catalyze the polymerization of monoolefins.Examples of Lewis Acid catalysts include AlCl₃, BF₃, BCl₃, TiCl₄, Al(C₂H₅)₃, Al(C₂ H₅)₂ Cl, and Al(C₂ H₅)Cl₂. Such carbocationic polymerizationcatalysts have many advantages, including high yield, fast reactionrates, good molecular weight control, and utility with a wide variety ofmonomers. However, conventional carbocationic polymerization processestypically employ Lewis Acid catalysts in unsupported form. Hence, thesecatalysts, typically, cannot be recycled or reused in a cost effectivemanner.

In a typical carbocationic polymerization process, such as thecarbocationic polymerization of isobutylene, a catalyst feedstream in aliquid or gaseous form and a monomer feedstream are fed simultaneouslyinto a conventional reactor. In the reactor, the streams areintermingled and contacted under process conditions such that a desiredfraction of the monomer feedstream is polymerized. Then, after anappropriate residence time in the reactor, a discharge stream iswithdrawn from the reactor. The discharge stream contains polymer,unreacted monomer and catalyst. In order to recover the polymer, thecatalyst and unreacted monomer must be separated from this stream.Typically, there is at least some residue of catalyst in the polymerwhich cannot be separated. After separation, the catalyst is typicallyquenched and neutralized. The quenching and neutralization steps tend togenerate large quantities of waste which must typically be disposed ofas hazardous waste.

The recycling or reuse of Lewis Acid catalysts used in polymer processesis difficult because of the chemical and physical characteristics ofthese catalysts. For example, most Lewis Acid catalysts are non-volatileand cannot be distilled off. Other catalysts are in a solid particulateform and must be separated from the polymer stream by physicalseparation means. Some Lewis Acid catalysts are gaseous, such as BF₃.The gases can be recycled and reused, but with considerable difficulty,by utilizing gas-liquid separators and compressors.

There have been several attempts made to support Lewis Acid catalysts onthe surface of inorganic substrates such as silica gel, alumina, andclay. Although these approaches are somewhat successful in recycling theLewis Acid catalysts, there are several disadvantages associated withtheir use. One particularly strong disadvantage is that these approachesto supported catalysts generally produce only low molecular weightoligomers. Another disadvantage is that the catalysts (supported oninorganic substrates) typically leach out during the reaction since thecatalysts tend to not be firmly fixed to the supporting substrates.

Attempts to support Lewis Acid catalysts can be characterized as fallinginto two basic classes; namely, those which rely on physical adsorptionand those wherein the Lewis Acid chemically reacts with the support.

U.S. Pat. No. 3,925,495 discloses a catalyst consisting of graphitehaving a Lewis Acid intercalated in the lattice thereof.

U.S. Pat. No. 4,112,011 discloses a catalyst comprising galliumcompounds on a suitable support such as aluminas, silicas and silicaaluminas.

U.S. Pat. No. 4,235,756 discloses a catalyst comprising porous gammaalumina impregnated with an aluminum hydride.

U.S. Pat. No. 4,288,449 discloses chloride alumina catalysts.

U.S. Pat. Nos. 4,734,472 and 4,751,276 disclose a method for preparingfunctionalized (e.g., hydroxy functionalized) alpha-olefin polymers andcopolymers derived from a borane containing intermediate.

U.S. Pat. No. 4,167,616 discloses polymerization with diborane adductsor oligomers of boron-containing monomers.

U.S. Pat. No. 4,698,403 discloses a process for the preparation ofethylene copolymers in the presence of selected nickel-containingcatalysts.

U.S. Pat. No. 4,638,092 discloses organoboron compounds with strongaerobic initiator action to start polymerizations.

U.S. Pat. No. 4,342,849 discloses novel telechelic polymers formed byhydroborating diolefins to polyboranes and oxidizing the polymericboranes to form the telechelic dehydroxy polymer. No use of theresulting polymer to support Lewis Acid catalysts is disclosed.

U.S. Pat. No. 4,558,170 discloses a continuous cationic polymerizationprocess wherein a cocatalyst is mixed with a monomer feedstream prior tointroduction of the feedstream to a reactor containing a Lewis Acidcatalyst.

U.S. Pat. Nos. 4,719,190, 4,798,190 and 4,929,800 disclose hydrocarbonconversion and polymerization catalysts prepared by reacting a solidadsorbent containing surface hydroxyl groups with certain Lewis Acidcatalysts in halogenated solvent. The only disclosed adsorbents areinorganic; namely, silica alumina, boron oxide, zeolite, magnesia andtitania.

U.S. Pat. No. 4,605,808 discloses a process for producing polyisobuteneusing a complex of boron trifluoride and alcohol as catalyst.

U.S. Pat. No. 4,139,417, discloses amorphous copolymers of monoolefinsor of monoolefins and nonconjugated dienes with unsaturated derivativesof imides. In the preparation of the polymer the imide is complexed witha Lewis Acid catalyst.

Japanese Patent Application No. 188996/1952 (Laid Open No.J59080413A/1984) discloses a process for preparing a copolymer of anolefin and a polar vinyl monomer which comprises copolymerizing anolefin with a complex of the polar vinyl monomer and a Lewis acid.

European Patent Application No. 87311534.9 (Publication No. EPA 0274912)discloses polyalcohol copolymers made using borane chemistry.

T. C. Chung and D. Rhubright, Macromolecules, Vol. 24, 970-972, (1991)discloses functionalized polypropylene copolymers made using boranechemistry.

T. C. Chung, Journal of Inorganic and Organometallic Polymers, Vol. 1,No. 1, 37-51, (1991) discloses the preparation of polyboranes and boranemonomers.

U.S. Pat. No. 4,849,572 discloses a process for preparing polybuteneshaving enhanced reactivity using a BF₃ catalyst. Polybutene is producedwhich has a number average molecular weight in the range of from 500 to5,000. The polymer has a total terminal double-bond content of at least40% based on total theoretical unsaturation of the polybutene. Thepolybutene contains at least 50% by weight isobutylene units based onthe polybutene number average molecular weight. The process isaccomplished by contacting a feed supply comprising at least 10% byweight isobutylene based on the weight of the feed with a BF₃ catalystunder conditions to cationically polymerize the feed in liquid phase toform polybutene. The polymer is immediately quenched with a quenchmedium sufficient to deactivate the BF₃ catalyst.

There has been a continuous search for catalysts having high efficiencywhich can be recycled or reused in cationic polymerization processes.The present invention was developed pursuant to this search.

SUMMARY OF THE INVENTION

One aspect of the present invention provides immobilized Lewis Acidcatalyst, comprising polymer having at least one Lewis Acid immobilizedwithin the structure therein, said polymer having repeating monomerunits represented by the structural formula:

    --[A].sub.a --[B].sub.b --[C].sub.c --

wherein

a represents about 1 to about 99 mole %,

b represents about 0 to about 50 mole %,

c represents about 1 to about 99 mole %,

a+b+c is preferably about 100%; ##STR3## C is selected from the groupconsisting of: ##STR4## combinations thereof. D is OH, halide, OR⁴, NH₂,NHR³, OM', or OM";

E is the residue of the reaction of at least one Lewis Acid with the Dsubstituent of monomer unit B;

R¹ represents a hydrogen ion (i.e., a proton), a C₁ -C₂₄ alkyl group(e.g., preferably C₁ -C₁₂, more preferably C₁ -C₄), or a C₃ -C₂₄ cycloalkyl group;

R² represents a C₁ -C₂₄ alkylene group (e.g., C₁ -C₁₀, more preferablyC₃ -C₅), a C₃ -C₂₄ cyclo alkylene group, a C₆ -C₁₈ arylene group, or aC₇ -C₃₀ alkylarylene group;

R³ represents a C₁ -C₂₄ alkyl group (e.g., preferably C₁ -C₁₂, and morepreferably C₁ -C₄), a C₃ -C₂₄ cyclo alkyl group, a C₁ -C₂₄ aryl group,or a C₇ -C₃₀ alkylaryl group;

R⁴ represents a C₁ -C₂₄ alkyl group (e.g., more typically C₁ -C₁₂,preferably C₁ -C₄), a C₃ -C₂₄ cyclo alkyl group, a C₁ -C₂₄ aryl group,or a C₇ -C₃₀ alkylaryl group;

M' represents alkali metal;

M" represents alkaline-earth metal.

The immobilized catalyst is derived from: a functionalized copolymerhaving the formula--[A]_(a) --[B]_(d) --, wherein A, B and a are definedas above. "d" represents about 1 to about 99 mole percent and is equalto the sum of b plus c. The functionalized copolymer has a numberaverage molecular weight of from 300 to 10,000,000, preferably 3,000 to10,000,000, more preferably 3,000 to 3,000,000, yet more preferably3,000 to 100,000, yet more preferably greater than 5,000 to 10,000 andmost preferably greater than 10,000 to 45,000 with a particularly usefuland preferred functionalized copolymer having a number average molecularweight of about 35,000.

A particularly preferred immobilized catalyst has a "b" of substantiallyzero mole percent, and R² which is a C₃ to C₆ alkylene group. Thepreferred immobilized catalyst is a solid having a particle size of from0.001 to about 1.0 millimeters and more preferably from 0.01 to about0.5 millimeters in average diameters.

Another aspect of the present invention relates to a process for usingthe above immobilized Lewis Acid catalyst. The catalysts can be used toproduce both high and low molecular weight polymer products, atrelatively high reaction temperatures.

In a preferred embodiment of the above process at least one inlet streamcomprising monomer feed to be polymerized is fed to a reactor having atleast one discharge stream. The monomer feed is polymerized in thereactor in the presence of the above-described immobilized Lewis Acidcatalyst. The resulting polymerized polymer product is removed from thereactor along with unreacted monomers in the discharge stream while theimmobilized catalyst is retained in the reactor.

The present invention includes cationically polymerized polymer productmade using the immobilized catalyst of the present invention. Suchpolymers can be made at any suitable molecular weights with preferredranges being from 300 to 1,000,000, more preferably 300 to 500,000number average molecular weight. The polymer product preferably has amolecular weight distribution ranging from 1.1 to about 8.0. However,narrower weight distributions of 1.8 to 3, and preferably 1.8 to 2.5 canbe made. The molecular weight and molecular weight distribution can betailored to particular uses. Useful polymers made using the immobilizedcatalyst can have number average molecular weights of from 300 to 5,000and more preferably from 500 to 2500 for use to make materials such asdispersion aids for lubricating oil compositions. Higher molecularweight polymers having a molecular weight of from 10,000 to 100,000, andpreferably from 20,000 to 80,000 are useful to prepare viscosityimprovers for lubricating oil compositions.

Yet another aspect of the present invention relates to a process foralkylating an organic substrate with alkylating agent by contacting amixture of substrate and alkylating agent in the presence of the abovedescribed immobilized Lewis Acid catalyst under alkylation conditions.

The substrate to be alkylated can be, for example, olefin, alkane, alkylhalides, aromatic, substituted aromatic or multi-substituted aromatic,and mixtures, and the alkylating agent can be olefin, alkane, alkylhalide, aromatic hydrocarbon, hydroxyaromatic hydrocarbon and mixtures;subject to the proviso that the alkylating agent is different from thesubstrate employed, e.g., if the substrate is an olefin, the alkylatingagent is not an olefin.

The present invention also includes a process for manufacturing theabove-described immobilized Lewis Acid catalyst. In this processfunctionalized copolymer having monomer units represented by theformula: --[A]_(a) --[B]_(d) -- is reacted with Lewis Acid catalyst toproduce the above-described immobilized Lewis Acid catalyst. A, B, a andd are defined above.

The immobilized catalysts and processes of the present invention offer anumber of advantages over conventional cationic catalysts andpolymerization processes.

A significant advantage of such immobilized catalysts is that they canbe reused. That is, they are usable for multiple polymerization cycles(in the context of a batch process) without regeneration, resulting insubstantial cost savings, as well as the elimination of significantamounts of hazardous waste typically generated in conventional LewisAcid processes. Not only can the immobilized Lewis Acid catalysts of thepresent invention be employed for multiple polymerization cycles, or ona continuous basis for extended polymerization times, but they can alsobe easily regenerated after they have been deactivated from prolongeduse. The catalyst life (before regeneration is required) will dependupon the reaction conditions, and in particular, contaminants present inthe feed streams which may poison the immobilized catalyst. In theory,no regeneration should be needed; however, in practice, poisons areusually present. Surprisingly, even when the immobilized catalysts arepartially poisoned, they continue to operate at high efficiencies whichare believed to exceed 70%. Not only does this result in significantcost savings, but the environmental impact of the process is minimized.

Another surprising and unexpected advantage of the present invention isthat cationic polymerization processes, utilizing the immobilizedcatalysts, can typically be operated, depending upon the desiredmolecular weight of the polymer, at relatively higher temperatures,compared to polymerization processes using conventional, butnon-immobilized, Lewis Acid catalysts. For example, conventionalcarbocationic polymerization processes for polybutene requiretemperatures in the range of -10° C. to +10° C., to produce polymershaving Mn of about 500 to 3,000 requiring extensive refrigerationsystems which are costly to operate. The processes of the presentinvention can be run at +5° C. to +35° C. to produce similar molecularweight polymers. Thus, the immobilized Lewis Acid catalyst appears to bemore efficient than catalysts of the prior art.

Yet another surprising and unexpected advantage of the present inventionis that gaseous catalysts such as BF₃ can now be immobilized. It is nowpossible to utilize BF₃ in a cationic process in a solid form by usingthe immobilized catalysts of the present invention. The benefits of BF₃can now be realized without the hazards and environmental liabilitiesthat are attendant with the use of gaseous BF₃. For example, aby-product of gaseous BF₃ in a cationic process is HF. Moreover, it isextremely difficult to recycle gaseous BF₃ since the BF₃ which isseparated from a reactor discharge stream contains gaseous monomerswhich often dimerize or oligomerize during recycle.

Another advantage of the immobilized catalysts of the present inventionis that the catalysts are easy to dispose of in an environmentallyadvantageous manner. The Lewis Acid catalyst, which typically containsmetals, can be stripped from the immobilized catalyst leaving behind afunctionalized copolymer, e.g., polyolefin thermoplastic copolymer. Thepolyolefin thermoplastic copolymer can then be disposed of substantiallywithout metal contamination.

Another advantage of the immobilized catalysts of the present inventionis that they can be easily removed from reactors. One method of removalinvolves simply raising the temperature inside the reactor to atemperature above the melting point of the polymer in which the LewisAcid is immobilized. The immobilized catalyst then melts and is easilywithdrawn from the reactor.

The novel structure of the immobilized catalysts of the presentinvention can result in enhanced activity for polymerization andalkylation processes when the Lewis Acid catalyst, represented bysubstituent E in the above formula, is separated by at least one carbonatom and preferably more than one carbon (e.g., 4) from the polymerbackbone. Without wishing to be bound by any particular theory, it isbelieved that orientation of the active catalyst sites is achieved(under the above situation), in such a manner as to facilitate contactof these sites with the monomer being polymerized. The favorableorientation is believed to result from increased mobility of the activecatalyst sites when they are located at the end of a flexible carbonatom or carbon chain. Favorable orientation of catalyst sites enhancespolymerization and alkylation activity. The novel structure of theimmobilized catalysts of the present invention is believed to rendereach such favorably oriented Lewis Acid catalyst site an active catalystsite. There is little or no interference between neighboring immobilizedLewis Acid catalyst sites. When such interference exists, it can causethe catalysts to effectively "shut-down".

Still another advantage of the Lewis Acid catalysts of the presentinvention is that they can be used in most polar or non-polar organicsolvents. The immobilized catalysts do not require that their use belimited to specific solvents. Useful solvents can include: hexane,heptane, butane,C₃₋₂₄ hydrocarbyl, and halogenated solvents such ashalogenetic hydrocarbons such as methylene chloride, dichloromethane,ethyl chloride and methyl chloride.

Still yet another advantage of the immobilized catalysts of the presentinvention is that they may be regenerated in situ, e.g., in a reactor bywashing with an acid and then treating with at least one Lewis Acidreagent.

The regeneration process is quite simple and can be done at relativelylow temperatures (even ambient temperatures) in the reactor vesselwithout having to remove the immobilized catalyst from the reactorvessel. It is believed that in situ regeneration is not practical withLewis Acid catalysts supported on inorganic substrates because of thenumber and nature of steps involved.

Yet another advantage of the immobilized Lewis Acid catalysts of thepresent invention is that minimal amounts of catalyst residues carryover to the polymer product. In comparison to a "once through" cationiccatalyst process, the polymers produced using the immobilized catalystsand processes of the present invention are virtually free of catalystresidues.

The foregoing and other features and advantages of the present inventionwill become more apparent from the following description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1: Formula for "hydroxylated polypropylene" and schematicperspective of the "Brush" arrangement of chains hydroxylatedpolypropylene. X represents halogen ions, or alkyl halide ions.

FIG. 2: ¹ H NMR spectrum of PIB prepared by catalyst A(PP--O--AlCl₂) atroom temperature. FIG. 2A is a magnified scale (100 times) of thespectrum from 4.0 to 6.0.

FIG. 3: ¹ H NMR spectrum of PIB prepared by catalyst C(PB--O--BF₂) at 0°C. FIG. 3A is a magnified scale (100 times) of the spectrum from 4.0 to6.0 ppm.

FIG. 4: ²⁷ Al spectrum of an unmobilized catalyst derived fromhydroxylated polypropylene and aluminum ethyl dichloride (Example 54).FIG. 4A is a comparative spectrum of the reaction product of 1-pentanoland aluminum ethyl dichloride.

FIG. 5: ²⁷ Al NMR spectrum of an unmobilized catalyst derived fromhydroxylated polybutene and aluminum diethyl chloride (Example 54). FIG.5A is a comparative spectrum of the reaction product of 1-pentanol andaluminum ethyl dichloride.

FIG. 6: ²⁷ Al NMR spectrum of an unmobilized catalyst derived fromhydroxylated polybutene and BF₃ (Example 59). FIG. 6A is a comparativespectrum of the reaction product of 1-pentanol and aluminum ethyldichloride.

FIG. 7: Is a schematic diagram of the experimental apparatus of Examples54-57.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Those skilled in the art will be able to appreciate the presentinvention by the following detailed description of the preferredembodiments. The present invention relates to an immobilized catalystsand process for preparing such a catalyst. The catalyst is particularlyuseful in the preparation of a variety of homopolymers and copolymers.

The novel immobilized catalysts of the present invention can be used topolymerize a variety of monomers into homopolymers and copolymers, e.g.,polyalkenes. The monomers include those having unsaturation which areconventionally polymerizable using carbocationic Lewis Acid catalystpolymerization techniques, and monomers which are the equivalentsthereof. The terms cationic and carbocationic are used interchangeablyherein. Olefin monomers useful in the practice of the present inventionare polymerizable olefin monomers characterized by the presence of oneor more ethylenically unsaturated groups (i.e., >C═C<); that is, theycan be straight or branched: monoolefinic monomers, such as vinylethers, ethylene, propylene, 1-butene, isobutylene, and 1-octene, orpolyolefinic monomers. Polyolefinic monomers include cyclic or acryclic,conjugated or non-conjugated, dienes.

Suitable olefin monomers are preferably polymerizable terminal olefins;that is, olefins characterized by the presence in their structure of thegroup >C═CH₂. However, polymerizable internal olefin monomers (sometimesreferred to in the patent literature as medial olefins) characterized bythe presence within their structure of the group ##STR5## can also beused to form polymer products. When internal olefin monomers areemployed, they normally will be employed with terminal olefins toproduce polyalkenes which are interpolymers. For purposes of theinvention, when a particular polymerized olefin monomer can beclassified as both a terminal olefin and an internal olefin, it will bedeemed to be a terminal olefin. Thus, 1,3-pentadiene (i.e., piperylene)is deemed to be a terminal olefin for purposes of this invention.

Preferred monomers used in the method for forming a polymer inaccordance with the present invention are preferably selected from thegroup consisting of ethylene and alpha-olefins and typically C₃ -C₂₅alpha olefins. Suitable alpha-olefins may be branched or straightchained, cyclic, and aromatic substituted or unsubstituted, and arepreferably C₃ -C₁₆ alpha-olefins. Mixed olefins can be used (e.g., mixedbutenes).

The alpha-olefins, when substituted, may be directly aromaticsubstituted on the 2-carbon position (e.g., moieties such as CH₂═CH--φ-- may be employed). Representative of such monomers includestyrene, and derivatives such as alpha methyl styrene, paramethylstyrene, vinyl toluene and its isomers.

In addition, substituted alpha-olefins include compounds of the formulaH₂ C═CH--R--X' wherein R represents C₁ to C₂₃ alkyl, preferably C₁ toC₁₀ alkyl, and X' represents a substituent on R and C can be aryl,alkaryl, or cycloalkyl. Exemplary of such X' substituents are aryl of 6to 10 carbon atoms (e.g., phenyl, naphthyl and the like), cycloalkyl of3 to 12 carbon atoms (e.g., cyclopropyl, cyclobutyl, cyclohexyl,cyclooctyl, cyclodecyl, cyclododecyl, and the like), alkaryl of 7 to 15carbon atoms (e.g., tolyl, xylyl, ethylphenyl, diethylphenyl,ethylnaphthyl, and the like). Also useful are bicyclic, substituted orunsubstituted, olefins, such as indene and derivatives, and bridgedalpha-olefins of which C₁ -C₉ alkyl substituted norbornenes arepreferred (e.g., 5-methyl-2-norbornene, 5-ethyl-2-norbornene,5-(2'ethylhexyl)-2-norbornene, and the like).

Illustrative non-limiting examples of preferred alpha-olefins arepropylene, 1-butene, 1-pentene, 1hexene, 1-octene, and 1-dodecene.

Dienes suitable for purposes of the present invention can be straightchain, hydrocarbon di-olefins or cycloalkenyl-substituted alkenes,having about 6 to about 15 carbon atoms, for example:

A. straight chain acyclic dienes, such as 1,4-hexadiene and1,6-octadiene;

B. branched chain acyclic dienes, such as 5-methyl-1,-4-hexadiene;3,7-dimethyl-1,6-octadiene; 3,7dimethyl-1,7-octadiene; and the mixedisomers of dihydro-myricene and dihydro-ocinene;

C. single ring cyclic dienes, such as 1,3-cyclopentadiene;1,4-cyclohexadiene; 1,5-cyclooctadiene and 1,5-cyclododecadiene;

D. multi-ring cyclic fused and bridged ring dienes, such astetrahydroindene; methyltetrahydroindene; dicyclopentadiene;bicyclo-(2.2.1)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl andcycloalkylidene norbornenes, such as 5-methylene-2-norbornene,5-propenyl2-norbornene, 5-isopropylidene-2-norbornene,5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, and5-vinyl-2-norbornene;

E. cycloalkenyl-substituted alkenes, such as allyl cyclohexene, vinylcyclooctene, allyl cyclodecene, vinyl cyclododecene.

Of the non-conjugated dienes typically used, the preferred dienes aredicyclopentadiene, methyl cyclopentadiene dimer, 1,4-hexadiene,5-methylene-2-norbornene, and 5-ethylidene-2-norbornene. Particularlypreferred diolefins are 5-ethylidene-2-norbornene and 1,4hexadiene.

The polymer and copolymer product which can be manufactured by theprocess of the present invention are those which can be manufactured bya carbocationic polymerization process and include but are not limitedto polyalkenes, such as polyisobutene, poly (1-butene), polyn-butene,polystyrene, ethylene alpha-olefin copolymers, and the like. The termcopolymer as used herein is defined to mean a polymer comprising atleast two different monomer units.

In particular, the immobilized catalysts of the present invention areespecially useful for manufacturing polyisobutene, poly(1-butene) andpoly-n-butene from feedstreams containing butene monomers. It isespecially preferred to use refinery feed streams containing C₄monomers, commonly referred to as Raffinate I and Raffinate II.

The Lewis Acids which can be immobilized as described herein to make thecatalysts of the present invention are defined herein to include any ofthose Lewis Acids known in the art to be capable of cationicallypolymerizing olefins in accordance with conventional techniques, andequivalents thereof. Suitable Lewis Acids typically include the halidesand alkyl compounds of the elements in Column III B and III A to VI A ofthe Periodic Table of the Elements including alkyl aluminum, aluminumhalides, boron halides, transition metal halides, and combinationsthereof. It is particularly preferred to use AlR_(n) X_(3-n) (n=0-3)wherein R is C₁ -C₁₂ alkyl or aryl and X is a halide, for example, Al(C₂H₅)₃, Al(C₂ H₅)₂ Cl, Al(C₂ H₅)C12, and AlCl₃, BF₃, BCl₃, FeCl₃, SnCl₄,SbCl₅, AsF₅, AsF₃, and TiCl₄.

The preferred catalysts are Lewis Acids based on metals from Group IIIA, IV B and V B of the Periodic Table of the Elements, including, butnot limited to, boron, aluminum, gallium, indium, titanium, zirconium,vanadium, arsenic, antimony, and bismuth. The Group IIIA Lewis Acidshave the general formula R_(n) MX_(3-n), wherein M is a Group III Ametal, R is a monovalent hydrocarbon radical selected from the groupconsisting of C₁ to C₁₂ alkyl, aryl, alkylaryl, arylalkyl and cycloalkylradicals; n is a number from 0 to 3; X is a halogen independentlyselected from the group consisting of fluorine, chlorine, bromine, andiodine. Non-limiting examples include aluminum chloride, aluminumbromide, boron trifluoride, boron trichloride, ethyl aluminum dichloride(EtAlCl₂), diethyl aluminum chloride (Et₂ AlCl), ethyl aluminumsesquichloride (Et₁.5 AlCl₁.5), trimethyl aluminum, and triethylaluminum. The Group IVB Lewis Acids have the general formula MX₄,wherein M is a Group IVB metal and X is a ligand, preferably a halogen.Non-limiting examples include titanium tetrachloride, zirconiumtetrachloride, or tin tetrachloride. The (group V B Lewis Acids have thegeneral formula MXy, wherein M is a Group V metal, X is a ligand,preferably a halogen, and y is an integer from 3 to 5. Non-limitingexamples include vanadium tetrachloride and antimony pentafluoride. TheLewis Acid immobilized in accordance with the present invention willpreferably be used during immobilization in gaseous or liquid form,either neat or as a solution using organic solvents. The Lewis Acid maybe used singly (i.e., one particular Lewis Acid catalyst) or incombination (i.e., two or more Lewis Acid catalysts).

Typical of Lewis Acid catalysts useful in the practice of the presentinvention are those having the formula MX_(m') (R^(5'))_(p') asillustrated in the Table, wherein m'=(the coordination of number ofM)-(p'+1); p'=0 to 3; and, R^(5') is C₁ -C₁₂ alkyl, C₆ -C₁₈ aryl, C₇-C₁₉ alkylaryl, and C₃ -C₁₅ cyclic or acyclic.

                  TABLE                                                           ______________________________________                                        MX.sub.m' (R.sup.5').sub.p'                                                   M      X         m'       R.sup.5'   p'                                       ______________________________________                                        Sb     Cl        5        --         0                                        Sb     Cl        3        --         0                                        Sb     F         5        --         0                                        Sn     Cl, Br    4        --         0                                        V      Cl        4        --         0                                        Be     Cl        2        --         0                                        Bi     Cl        3        --         0                                        Zu     Cl        2        --         0                                        Cd     Cl        2        --         0                                        Hg     Cl        2        --         0                                        As     F         3        --         0                                        AS     F         5        --         0                                        Nb     F         5        --         0                                        Ta     F         5        --         0                                        Ga     Cl, Br    3        --         0                                        In     Cl, Br    3        --         0                                        Ti     Br, Cl    4        --         0                                        Zr     Cl        4        --         0                                        W      Cl        5        --         0                                        B      F, Cl, Br, I                                                                            3        --         0                                        Fe     Cl, Br    3        --         0                                        Al     Cl, Br, I 3        --         0                                        Al     Cl, Br, I 3        C.sub.1 to C.sub.12 alkyl,                                                               0-3                                                                aryl, alkylaryl,                                                              cyclic or acyclic                                   ______________________________________                                    

Lewis Acids useful as catalysts in carbocationic processes as well ascarbocationically polymerizable monomers, and, the polymers producedfrom such processes are disclosed and described in the followingpublications: 1) Cationic Polymerization of Olefins: A CriticalInventory, Kennedy, Joseph P., John Wiley & Sons, New York (1975), and,2) Carbocationic Polymerization, Kennedy, Joseph P., John Wiley, & Sons,New York (1982).

The immobilized Lewis Acid catalysts of the present invention may beused singly or in combination with cocatalysts. The cocatalysts includematerials known in this art such as water, alcohols, Bronsted Acids, forexample, anhydrous HF or HCl, and alkyl halides, for example, benzylchloride or tertiary butyl chloride.

The immobilized catalysts of the present invention are derived frompolymers, preferably polyolefin thermoplastic copolymers, havingfunctionalized monomers incorporated into the structure thereof. Suchfunctionalized copolymers can be represented by the following structuralformula:

    --[A].sub.a --[B].sub.d --                                 (I)

wherein "A" represents unfunctionalized monomer unit, and "B" representsthe functionalized monomer unit in the copolymer wherein: ##STR6## R¹which can be the same or different represents a hydrogen ion (i.e., aproton), an alkyl group, preferably a C₁ -C₂₄ alkyl group, and morepreferably C₁ -C₄ alkyl group, or a cyclo alkyl group, preferably a C₃-C₂₄ cyclo alkyl group, and more preferably C₅ -C₈ cyclo alkyl group;

and, ##STR7## wherein D, which represents the functional portion ofmonomer unit B, can be OH, halide, NH₂, OR⁴, NHR³, OM', or OM"

R², which can be the same or different represents an alkylene group,preferably a C₁ -C₂₄ alkylene group, more preferably a C₃ -C₅ alkylenegroup, a cyclo alkylene group, preferably a C₆ -C₂₄ cyclo alkylenegroup, an arylene group, preferably, a C₆ -C₁₈ arylene group, or, analkarylene group, preferably a C₇ -C₃₀ alkylarylene group;

R³, which can be the same or different represents an alkyl group,preferably a C₁ -C₂₄ alkyl group, preferably a C₁ -C₄ alkyl group, acyclo alkyl group, preferably a C₃ -C₂₄ cyclo alkyl group, morepreferably a C₅ -C₈ cyclo alkyl group, an aryl group, preferably a C₆-C₁₈ aryl group, or, an alkaryl group, preferably a C₇ -C₃₀ alkarylgroup;

R⁴, which can be the same or different represents an alkyl group,preferably a C₁ -C₂₄ alkyl group, more preferably a C₁ -C₄ alkyl group,a cyclo alky group, preferably a C₃ -C₂₄ cyclo alkyl group, an arylgroup, preferably a C₆ -C₁₈ aryl group, or, an alkaryl group, preferablya C₇ -C₃₀ alkylaryl group;

a and d represent the mole % of each respective monomer unit A and B inthe functionalized copolymer with "d" representing the sum of b and c informula III below, the sum of a+d being 100 mole %;

M' represents alkali metal;

M" represents alkaline-earth metal.

The functionalized copolymers are typically prepared from boratedcopolymers which are then treated to replace the boron with functionalgroups represented by D in formula I in the following manner. Morespecifically, sufficient amounts (i.e., sufficient to eventually yieldthe desired amounts and ratios depicted by a, b, and c, in formula IIIbelow) of suitable alpha-olefin monomers (A) and suitable boranemonomers (B) (as defined hereinafter) can be reacted in a suitablereactor using Ziegler-Natta catalysis under sufficient reactionconditions effective to form a borated, preferably thermoplastic,copolymer. The Ziegler-Natta polymerization may be catalyzed withconventional Ziegler-Natta catalysts or equivalents thereof such asTiCl₃ AA/Al(Et)₃ or a transition metal halide of Groups IV to VIII ofthe Periodic Table of the Elements and a cocatalyst which is an alkylcompound including alkyl halides of a metal of Groups I to III of thePeriodic Table of the Elements and the like. The abbreviation "AA" usedherein is defined to mean "alumina activated". Activated aluminas arewidely known and used in adsorption and catalysis because of their largesurface area, pore structure, and surface chemistry. They are made bythe controlled heating of hydrated aluminas. The activated alumina canbe used as a catalyst support. The use of activated alumina as acatalyst support is optional.

Non-limiting examples of the unfunctionalized monomer (A) alpha-olefinmonomers which may be used to prepare the functionalized copolymerintermediates useful to make the immobilized catalysts of the presentinvention include ethylene and C₃ -C₂₄ alpha-olefin monomers, such as,propylene, 1-butene, 1-pentene, 1-hexene, oligomers, co-oligomers, andmixtures thereof. Most preferred are propylene and 1-butene, thealpha-olefin monomers include any monomer, oligomer or cooligomerpolymerizable by Ziegler-Natta catalysis and equivalents thereof.

Suitable borane monomers, from which monomer unit B in formula I isderived, can be prepared by reacting a diolefin having the formula CH₂═CH--(CH₂)_(m) --CH═CH₂ (wherein m is about 1 to 10) with a dialkylborane solution. Non-limiting examples of diolefins include1,7-octadiene, 1,5-hexadiene, and 1,4-pentadiene. Non-limiting examplesof dialkyl borane solutions include 9-borabicyclo[3,3,1]nonane(hereinafter abbreviated as "9-BBN") in tetrahydrofuran, ethyl ether,methylene chloride, and the like. Borane monomers, useful in thepractice of the present invention, and methods of preparation, aredisclosed in U.S. Pat. Nos. 4,734,472 and 4,751,276 which areincorporated by reference. Preferred borane monomers useful in thepractice of the present invention will have the following formula:##STR8## where n=about 3 to 12 and R⁶ and R⁷ are the same or differentand are alkyl or cycloalkyl groups having about 1 to 10 carbon atoms.Non-limiting examples of borane monomers include B-7-octenyl-9-BBN,B-5-hexenyl-9-BBN, B-4-pentenyl-9-BBN and the like with the mostpreferred being B-5-hexenyl-9-BBN.

The borated copolymers, preferably thermoplastic copolymers, arefunctionalized prior to reacting with a Lewis Acid catalyst in order toform the functionalized copolymer from which the immobilized catalystsof the present invention are derived.

It is desireable to functionalize the borated polymer so that thecatalyst can be chemically bonded to it. However, if one were willing toaccept the attendant disadvantages, the borated copolymer may be reacteddirectly with Lewis Acid catalyst to form an immobilized catalyst. Thefunctional groups include halides, hydroxyls, carboxylic acid, NH₂ andmaterials having the formula OR⁴ and NHR³, wherein R³ and R⁴ are asdefined in formula I. It is especially preferred to utilize primaryfunctional groups such as hydroxide and halides. The preparation of thefunctionalized copolymers of the present invention is typicallyaccomplished by replacement (referred to herein as conversion) of boranegroups in the borated copolymer with the groups represented bysubstituent D in formula I by contact with a conversion agent. Suitableconversion agents include hydrogen peroxide/NaOH, NH₂ Cl, NH₂ SO₃ H,NaI/chloramine-t-hydrate/CH₃ CO₂ Na. It is particularly preferred to usehydrogen peroxide/NaOH when the desired functional group is hydroxyl,this latter embodiment being most preferred. The conversion agent andconversion conditions are selected to cleave the boron group from theborated thermoplastic and substitute a functional group in its place.The extent of conversion is determined by the eventual valves of c and bof formula III sought to be impacted to the immobilized catalyst.

Optionally, the functionalized copolymer intermediates of the presentinvention may be further reacted with an alkyl alkali metal or alkylalkaline-earth metal compounds to form an alternative functional groupmore easily reactable with certain Lewis Acids such as BF₃, prior toreaction with a Lewis Acid catalyst. These alternative functional groupsare depicted in formula I when D is OM' or OM".

Examples of alkyl alkali metal and alkyl alkaline-earth metal compoundsinclude butyl lithium, butyl sodium, butyl potassium, and ethylmagnesium. In general, the alkyl alkali metals will have the formulaM'R' wherein M' is an alkali metal and R' is a C₁ -C₂₄ alkyl group. Thealkali metals (Group I A of the Periodic Table) include lithium, sodium,potassium, rubidium, cesium and francium. In general the alkylalkaline-earth metal compounds will have the formula M"R" wherein M" isan alkaline-earth metal and R" is a C₁ -C₂₄ alkyl group. Thealkaline-earth metals (Group II A of the Periodic Table of the Elements)include calcium, barium, magnesium, strontium and rhodium. Thus, theterm functionalized copolymer as used herein is intended to includefunctionalized copolymers which are further reacted with an alkyl alkalior alkaline earth metal compounds.

A stoichiometrically idealized reaction sequence for the preparation ofa completely functionalized copolymer (i.e. b→0) from alpha-olefinmonomers (A) and borane monomers (B), e.g., a functionalized copolymerderived from propylene and having a borane monomer having unitscompletely reacted to have hydroxyl functionality or halidefunctionality, is as follows: ##STR9##

The term "AA" has been previously defined to mean alumina activated.

The functionalized copolymers are typically synthesized to be insolublein common organic solvents at room temperature and stable under typicalcationic polymerization conditions. The functionalized copolymers willtypically have a number average molecular weight (Mn) in the rangebetween 300 to 10,000,000, preferably 3,000 to 3,000,000, morepreferably 3,000 to 1,000,000, yet more preferably greater than 3,000 to100,000, even more preferably greater than 5,000 to 50,000 and mostpreferably greater than 10,000 to 45,000, with a particularly useful andpreferred functionalized copolymer having an (Mn) of about 35,000.

The immobilized catalysts of the present invention will typically beprepared from the functionalized copolymer in the following manner.

A sufficient amount of at least one Lewis Acid catalyst, preferably inexcess, is mixed with a sufficient amount of a functionalized copolymerin a suitable reactor vessel under suitable reaction conditionseffective to react the functionalized copolymer with the Lewis Acidcatalyst thereby producing the immobilized catalyst as defined informula III. By "excess" is meant a molar ratio of Lewis Acid catalystto functional groups of about more than 1:1, preferably 5:1. Thereaction is preferably carried out at a temperature of about 20° C. to110° C. although the reaction temperature may range from about -50° C.to 200° C. The reaction is preferably carried out by dissolving theLewis Acid catalyst in a thoroughly dried, inert solvent selected fromany suitable solvents including alkanes, aromatic solvents and alkylhalides; however, the Lewis Acid catalyst may be in the gas phase orliquid phase when reacted with the functionalized copolymer. Thepreferred solvents will be good solvents for the Lewis Acid catalyst andwill also be relatively good solvents (swellable) for the polymersubstrate to maximize the penetration of reagent into the polymermatrix. Immobilized catalysts are not readily extractable by the solventand by reaction media.

The resulting immobilized Lewis Acid catalysts of the present inventioncan be described as comprising polymer having at least one Lewis Acidimmobilized within the structure thereof, said polymer having monomerunits represented by the structural formula:

    --[A].sub.a --[B].sub.b --[C].sub.c --                     (III)

wherein a+b+c represents the respective mole % of monomer units A, B,and C in said polymer with the sum of a+b+c preferably being about 100%,and wherein

a represents about 1 to about 99 mole %

b represents about 0 to about 50 mole %

c represents about 1 to about 99 mole %

A, B, are as described in connection with formula I; C is selected fromthe group consisting of: ##STR10## combinations thereof. wherein:

E is the residue of the reaction of a Lewis Acid with the D functionalsubstituent in monomer unit B; and

R² is as described in formula I.

When monomer Unit B in formula I remains unconverted, the D substituentremains unchanged and monomer unit B in formula I becomes monomer unit Bin formula III. In contrast, when D in monomer unit B is acted upon bythe conversion agent, monomer unit B becomes monomer unit C byreplacement of substituent D with substituent E (i.e., the Lewis Acidresidue).

As indicated above, E is defined as being the residue of the reaction ofa Lewis Acid Catalyst with the D functional group of monomer unit B. Itwill be appreciated by those skilled in the art that the precise formulafor E will vary depending upon the Lewis Acid catalysts used and thefunctional groups present on the functionalized copolymer.

The ratio of a:c in formula III will typically be about 1:1 to about100:1, more typically about 5:1 to about 100:1, and preferably about20:1 to about 50:1. The ratio of b:c will typically be about 0.1:1 toabout 20:1, more typically about 0.1:1 to about 10:1, and preferablyabout 0.5:1 to about 5:1. Where all of the D reacts to form E, than bbecomes 0. In a preferred embodiment substantially all of the D isreacted to form E.

Although the immobilized catalysts of the present invention comprise aLewis Acid chemically reacted with and chemically bonded to a copolymerbackbone, there is at least one instance wherein the bond is a pi (π)complex. Specifically, when D is hydroxyl and the Lewis Acid intended toreplace D is BF₃, then the BF₃ will form a pi (π) bond with thecopolymer backbone by complexing with hydroxyls contained in thecopolymer.

The immobilized Lewis Acid catalysts of the present invention willtypically have, prior to any processing, a particle-like structurewherein each particle consists of an immobile copolymer backbone andsubstituent Lewis Acid. While not wishing to be bound to any particulartheory, it is believed that the Lewis Acid tends to predominate on thesurface of the particle, while the interior of the particle will tend toconsist primarily of immobile crystalline copolymer. More specifically,when the borated copolymer intermediate is prepared prior to forming thefunctionalized copolymer, the difference in reactivity between theborane comonomer (lower activity) and olefin comonomer (higher activity)is believed to result in a predominantly block or sharply taperedcopolymer. It is believed to be important that the non-boron containingblock be crystalline, since as the block crystalizes, it forms aparticle having a crystalline core. During crystallization the boronmonomer block migrates or orients at the particle surface, therebyensuring eventual predominance of the Lewis Acid sites at the surface ofthe particle. This orientation phenomena is maintained even upon meltextrusion of the immobilized catalyst and becomes even more pronouncedin the final catalyst due to the high polar character of the Lewis Acid.This structure results in catalysts having good polymerization activityand high surface area. Reference is made to FIG. I showing the formulaand speculated morphologic arrangement of hydroxylated polypropylene.

The immobilized catalysts of the present invention may be used forprolonged periods of time and then regenerated. The catalyst may even beregenerated in situ in a reactor if so desired. The catalysts are easilyregenerated. The regeneration process is preferably accomplished byfirst washing the immobilized catalyst while in the reactor vessel withany Bronsted acid such as HCl, H₂ SO₄ and the like, and then treatingthe immobile, plastic phase of the immobilized catalyst with Lewis Acidreagents. Optionally, after the acid wash, and prior to treatment withthe Lewis Acid reagent, the immobilized catalyst is treated with analkyl alkali metal or an alkyl alkaline-earth metal compound to form anintermediate salt which is then treated with Lewis Acid catalystreagent. Typically, these Lewis Acid reagents will consist of Lewis Acidcatalyst solutions in organic solvents such as toluene, methylenechloride and the like. Preferably the strengths of the Lewis Acidcatalyst solution will range from about 10 wt. % to about 50 wt. %. Itis preferred to use an excess of Lewis Acid catalyst reagent in theregeneration process. By "excess" is meant from two to five times themole ratio of catalyst to functional groups. Rather than use solutionsof Lewis Acid catalysts, the Lewis Acid catalyst may be used in a liquidor gaseous form.

The immobile thermoplastic is stable under cationic reaction conditions;it is insoluble in hydrocarbon solvents below 500° C. and has highmechanical strength. One particularly preferred form of the immobilizedcatalyst is finely divided particles. The finely divided particles canbe obtained using various particle size reduction processes includingfreezing and pulverizing, and conventional particle size reductionprocesses.

While the polymer backbone of the immobilized catalysts of the presentinvention can exist as random copolymers, block copolymers, taperedcopolymers, graft copolymers and alternating copolymers, it isparticularly preferred to use immobilized catalysts of the presentinvention having a monomer distribution which is described as block orpredominantly tapered. It will be appreciated by those skilled in theart that the monomer configuration of the copolymer will affect itschemical and physical properties. The term copolymer as used herein isdefined to mean a polymer having two or more monomeric units. Themonomeric configuration in the polymer backbone is determined by anumber of factors well known to those skilled in this art, includingreactivity ratios, rates of monomer addition, sequencing, reactordesign, reaction conditions and the like.

As indicated above, it is believed to be highly advantageous that theimmobilized catalysts of the present invention exhibit crystallinity.The degree of crystallinity is directly related to the molar amount "a"of the monomer component [A] of formula I. Because of the advantages ofcrystallinity, it is desired to select monomer type and polymerizationconditions conducive to the formation of thermoplastic copolymer.

Typically the value of "a" will range from about 1 to 99 mole %, moretypically about 25 to 99 mole %, and preferably about 50 to 99 mole % ofthe immobilized catalyst backbone. It will be appreciated by thoseskilled in this art that the degree of crystallinity will increase withincreasing mole % of [A]. It will also be appreciated that the physicalcharacteristics of the immobilized catalysts of the present inventionwill be related, at least in part, to their degree of crystallinity. Forexample, a mole % of [A] greater than 50% will typically result in asolid phase immobilized catalyst.

There are various methods of determining when the desired crystallinityof the immobilized catalysts of the present invention is achieved. Oneindirect method is to react the boron in the boron-containing copolymer(prior to functionalization) with a Lewis base. The weight increase isindicative of the amount of boron present and the amount ofthermoplastic monomer units [A] present in the copolymer may then becalculated. As previously mentioned, when the mole % of [A] is about 50%or greater, the immobilized catalysts will exhibit desiredcrystallinity. In addition to the mole % of [A], the crystallinity is afunction of the amount of boron sites on the surface which can befunctionalized to react with a Lewis Acid. catalyst (i.e., an increasein the borated precursor of monomer unit B will decrease the amount ofmonomer unit A in the polymer). The number of surface boron sites can bemeasured by a variety of conventional analytical techniques. It ispreferred to use Boron NMR. In a preferred embodiment, most of the LewisAcid catalyst reactable sites depicted by D in formula I will be on thesurface of the functionalized thermoplastic copolymer.

One particularly preferred method of determining crystallinity is tomeasure the DSC (Differential Scanning Calorimetry) curve of a sample ofthe immobilized Lewis Acid catalyst. This will give the melting point ofthe sample, and, from the intensity of the peak of the curve, thecrystallinity can be calculated.

Access to any boron which may be present in the interior of theprecursor copolymer particles by the conversion agent is controlled byusing swellable solvents such as THF. By swellable solvents is meant asolvent which will diffuse into a functionalized copolymer. Examples ofsuch solvents include methylene chloride and toluene.

As previously mentioned, it is believed that, more likely than not, thecrystalline segments of the immobilized catalysts of the presentinvention tend to form an inner immobile crystalline phase while theLewis Acid sites and any other functionality which may be present tendto be oriented at the particle surface. Thus, the immobilized catalystretains at least some of the original physical properties of a purecrystalline polymer. For example, the crystallinity and thermalstability of an immobilized catalyst of the present invention will besimilar to that of the purely thermoplastic crystalline copolymer.

In addition, as previously mentioned, the immobilized catalyst of thepresent invention may be used in particle form. Typically, in apolymerization reaction the particle size of the immobilized catalystwill be about 0.001 mm to about 20.0 mm, more typically about 0.01 mm toabout 10.0 mm, and preferably about 0.01 mm to about 1.0 mm.

The catalyst can be formed to fine particles by suitable means.Preferably, the catalyst can be frozen by suitable means, such asliquefied compounds which are gaseous at ambient temperature such asnitrogen. The frozen catalyst can be comminuted to a fine particle size,preferably having a distribution of from about 0.001 mm to about 1.0 mmand more preferably from about 0.01 mm to about 0.5 mm. It has beenfound that the use of catalyst in the preferred range results in polymerof the present invention having greater terminal unsaturation andthereby greater reactivity. Particularly preferred polymer havinggreater terminal unsaturation are polybutenes including poly-n-butenesand polyisobutylene.

The catalyst may be processed according to conventional thermoplasticprocessing techniques such as molding, extruding, forming and coating toproduce various catalyst structures having optimal surface areas. Thecatalysts may be molded into various shapes such as column packing ringsand the like. It is contemplated that the catalysts of the presentinvention can be coated onto a variety of supporting substrates such asmetal, ceramic, plastics including thermoplastic, glass, fiberglass,carbon, graphite and the like. It is further contemplated that thesecatalysts can be extruded or molded onto such substrates.

In a typical molding process, the immobilized catalyst is fed to amolding machine having a heating means and cooling means. Theimmobilized catalyst is heated to a state where it is flowable (e.g., ator above glass transition temperature) and it is transported by the feedmeans to a mold having cavities therein. The plastic is transportedunder sufficient heat and pressure to fill in the cavities, cooled, andremoved, thereby retaining the shape of the cavities.

The coatings may be any conventional coating and equivalents thereofincluding, but not limited to, liquid polymer melts or solution polymercoatings. The coatings may also comprise dispersions, both aqueous andnonaqueous, enamels, lacquers, dry powders, and aqueous or organicelectrodeposition compositions. The coatings may be cured inconventional manners including heating, drying, crosslinking, andradiation. The coatings will contain conventional components andincipients such as solvents, resins, binders, dispersants and optionallypigments, mixing and flow agents, curing agents and the like. Thecoatings are prepared using conventional mixing, dispersing, andparticle size reduction processes and equipment such as stirred tanks,ball mills, shot mill, high shear mixers and the like.

It is contemplated that the surfaces of reactor vessels and processpiping and equipment may be coated with the immobilized catalysts of thepresent invention. In addition, reactor components such as packing maybe coated. Any conventional coating processes and equivalents thereofnay be used including, but not limited to, spraying, dipping, powdercoating, brushing, rolling, electrodeposition and the like.

Coatings, manufacturing processes, application processes, and, plasticsprocessing methods, products and process equipment are disclosed inKirk-Othmer Encyclopedia of Chemical Technology, Third Edition, JohnWiley & Sons, New York (1982).

The carbocationic polymerization process of the present invention may becarried out as a continuous, semi-continuous or batch process. Thereactors which may be utilized in the practice of the present inventioninclude conventional reactors and equivalents thereof such as batchreactors, stirred tank reactors, fluidized bed reactors, and continuoustank or tubular reactors and the like. As previously mentioned, theprocess may be continuous, batch or semi-continuous and combinationsthereof.

The reactor will contain sufficient amounts of the immobilized catalystof the present invention effective to catalyze the polymerization of themonomer containing feedstream such that a sufficient amount of polymerhaving desired characteristics is produced. The reaction conditions willbe such that sufficient temperature, pressure, and residence time aremaintained effective to produce the desired polymers having the desiredcharacteristics.

Typically, the catalyst to monomer ratio utilized will be thoseconventional in this art for carbocationic polymerization processes. Inthe practice of the present invention, the catalyst to monomer ratio isselected based on the ratio of residue E to monomer being polymerized.In the practice of the present invention the mole ratio of the residue Eto the monomer will typically be about 1/5000 to about 1/50, moretypically about 1/1000 to about 1/100, and preferably about 1/500 toabout 1/200. This mole ratio will be calculated by determining thenumber of Lewis Acid catalyst sites in the immobilized Lewis Acidcatalyst. This can be done by using conventional analytic testingtechniques such as elemental analysis, NMR (e.g., aluminum NMR) andabsorption spectroscopy. Once the number of Lewis Acid sites per unit ofimmobilized catalyst is known, the mole ratio is calculated in aconventional manner.

The reaction temperature will typically be maintained to about 50° C. toabout -30° C., more typically about 40° C. to about -20° C., andpreferably about 30° C. to about -10° C. The reaction pressure willtypically be about 200 k PA to about 1600 k PA, more typically about 300to about 1200, and preferably about 400 to about 1000. The degree ofpolyitierization of the monomer feedstream will typically be about 6 toabout 10,000, more typically about 10 to about 2,000, and preferablyabout 10 to about 500.

The yield of polymer is dependent on reaction time and catalyst particlesize. The cationic polymerization of a polymer such as isobutylene isrelated to the availability of catalyst group (i.e. E). The larger theimmobilized catalyst particle, the smaller the surface area of thecatalyst which is available. Small surface areas, preferably less than 1millimeter diameter particles are preferred for increased reaction rate.Nevertheless, the extent of reaction will continue to be high but withlarger particles with the total reaction taking a longer period of time.

The molecular weight of the polymer produced, preferably a polybutyleneusing a polyolefin immobile catalyst of the present invention has beenfound to be higher than using the corresponding Lewis Acids from whichthe immobilized catalysts are derived. For example, conventional LewisAcids such as AlCl₃, ethyl aluminum dichloride, diethyl aluminumchloride, and boron trifluoride used as catalysts for the reaction ofpolybutenes results in lower molecular weight polymer than if they areimmobilized. While not wishing to be bound to any theory, it isspeculated that the relatively higher molecular weight of polymer madeusing the immobilized catalyst of the present invention may be due toslow chain transfer because of stable carbocation in the immobilizedcatalyst. The alkoxide ligand denotes π-electron density to aluminumactive site and stabilizes the propagating center. This affect is verysignificant for catalysts having a immobilized structural unit of --O)₂AlEt species. As illustrated in the examples specific immobilizedcatalysts having at least some immobilized structure of aluminum ethylor aluminum diethyl result in higher molecular weight polymer.Therefore, the molecular weight of the polymer of the present inventiondepends on temperature, solvent type, and catalyst type.

A preferred combination of higher temperature and specific catalyststructure derived from a diethyl aluminum or aluminum type catalyst anda polar solvent results in higher molecular weights. A preferredimmobilized catalyst to achieve higher molecular weights is one using apolar solvent such as methylene dichloride, at a temperature of greaterthan -45° C. and preferably greater than -20° C. and most preferably ata temperature range of -30° to +10° C. An immobilized catalyst can bederived from a dialkylhalide Lewis Acid. Diethyl aluminum chloride ispreferred. Polymer using these preferred features have a mol(Bcularweight of greater than 10,000 and preferably greater than 20,000 numberaverage molecular weight.

In specific embodiments of the present invention cationicallypolymerized polymer having controlled and increased terminalunsaturation can be produced.

FIG. 2 shows the ¹ H NMR spectrum of polyisobutylene (PIB) which wasprepared by using immobilized AlCl₃ with a copolymer of propylene and1-hexenyl-6-ol (PP--O--AlCl₂) at room temperature. The overall spectrumis similar to those of found PIB prepared by soluble Al catalysts, suchas AlCl₃, EtAlCl₂, Et₂ AlCl, as well as C₅ --O--AlCl₂(1-hexenyl-6-AlCl₂) catalyst. Two major peaks are at 0.95 and 1.09 ppm,due to --CH₃ and --CH₂ protons in PIB polymer. There are some weak peakslocated in the olefinic region, between 4.5 and 6.0 ppm. The unsaturateddouble bond in polymer chain is the evidence of proton chain transferreaction during the polymerization. In conjunction with the gelpermeation chromatography (GPC) molecular weight studies, theintegrative intensity of olefinic region implies an average of a doublebond per polymer chain. In detail, (FIG. 2A), there are two quartets atabout 5.4 and 5.2 ppm and two singlets at about 4.9 and 4.6 ppm. Thesinglets at 4.9 and 4.6 ppm are indicative of two types of nonequivalentvinylidene hydrogens which may be located at the end of polymer chain.The quartets at 5.4 and 5.2 ppm are the olefinic hydrogens coupled tomethyl group, which are due to the internal double bonds. The ¹ H NMRpeak assignments are summarized in Table I.

                  TABLE I                                                         ______________________________________                                        Olefin Structures from .sup.1 H NMR Shifts                                    Structure         Observed .sup.1 H Chemical Shifts                           ______________________________________                                         ##STR11##        4.88, 4.66 singlet                                           ##STR12##        5.15 singlet                                                 ##STR13##        5.18 quartet                                                 ##STR14##        5.38 quartet                                                ______________________________________                                    

A significantly high amount of internal double bonds with variousstructures are present, which indicates carbocationic isomerizationtaking place by Lewis acid catalyst after the polymerization reaction.This olefin isomerization behaviors are similar to those in the solubleAl catalyst systems, such as AlCl₃ EtAlC₂, Et₂ AlCl.

A different ¹ H NMR spectra of PIB was observed by using immobilizedcatalyst BF₃ with a copolymer of butene-1 and 1-hexenyl-6-ol(PB--O--BF₂) at 25° and 0° C. The chemical shifts in double bond regionconsist of two major singlets at 4.9 and 4.6 ppm, corresponding toterminal double bond, and two small peaks at about 5.15 ppm,corresponding to internal double bond. (FIGS. 3, 3A) Comparing theintegrated intensities between olefinic peaks, shown in FIG. 3(A), thePIB prepared at 0° C. contains more than about 85% of terminal doublebonds than internal double bonds. The reason for such a high percentageof terminal double bonds in PB--O--BF₂ polymerization is not clear. Theproton transfer reaction (β-proton elimination) is the termination stepwhich can form both terminal and internal double bond as shown in thefollowing equation. ##STR15## The elimination of proton from twoterminal methyl groups are statistically favorable. However, theelimination of proton from the last methylene unit forms athermodynamically stable internal double bond. Theoretically, themaximum percentage of terminal double bonds in the final PIB can not bemore than 75%. it is speculated that some effects from the substratepolymer may play a role to control the termination reactions and toavoid any isomerization reactions. A control experiment, using C₅--O--BF₃ (1-hexenyl-6-BF₂) soluble catalyst under the same reactioncondition, resulted in more than 30 mole percent of internal doublebonds.

The PIB product with high concentration of terminal double bonds is avery desirable molecular structure, called "reactive PIB", which can beeasily functionalized under mild reaction conditions. The terminaldouble bonds react more easily with maleic anhydride than the internaldouble bonds. Internal unsaturated PIB preferably undergo a halogenationreaction before maleic anhydride reaction. Known "reactive PIB" have alow number average molecular weight (500-2000 g/mole) PIB with 60-70%terminal (or external) double bonds, which is prepared by BF₃ catalyst.Reference is made to U.S. Pat. No. 4,605,808 hereby incorporated byreference for a review of the reactivity of terminal unsaturation. Thepolymer of the present invention, preferably PIB, preferably contains atleast 60, preferably at least 70, more preferably at least 80 percent ofterminal double bonds.

The feedstock stream to this process may be at least one pure or mixedmonomer feedstream or combinations thereof. Additionally, the monomerfeedstream may be mixed with solvents such as hexane, methylenedichloride and the like. A preferred feedstock to this process may be apure or mixed refinery butene stream containing one or more of 1-butene,2-butene (cis and trans), and isobutene. The preferred feedstocks(preferred on an availability and economic basis) are available fromrefinery catalytic crackers and steam crackers. These processes areknown in the art. The butene streams typically contain between about 6wt. % and about 50 wt. % isobutylene together with 1-butene, cis- andtrans-2-butene, isobutane and less than about 1 wt. % butadiene. Oneparticularly preferred C₄ feedstream is derived from refinery catalyticor steam cracking processes and contains about 6-45 wt. % isobutylene,about 25-35 wt. % saturated butanes and about 15-50 wt. % 1- and2-butenes. Another preferred C₄ feedstream is referred to as RaffinateII characterized by less than about 6 wt. % isobutylene. The monomerfeedstream is preferably substantially anhydrous, that is, it containsless than 50 ppm, and more preferably less than about 30 ppm, and mostpreferably less than about 10 ppm, by weight of water. Such low levelsof water can be obtained by contacting the feedstream, prior to thereactor, with a water absorbent (such as CaCl₂, CaSO₄, molecular sievesand the like) or by the use of distillation drying. Suitable molecularsieves include 4 to 8 US mesh 3 Angstrom molecular sieves.

The monomer feedstream is typically substantially free of any otherimpurity which is adversely reactive with the catalyst under thepolymerization conditions. For example, the monomer feed to animmobilized catalyst should be preferably substantially free of bases(such as caustic), sulfur-containing compounds (such as H₂ S, COS, andorganomercaptans, e.g., methyl mercaptan, ethyl mercaptan), N-containingcompounds, and the like. Most preferably, the monomer feed contains lessthan about 10 ppm by weight of sulfur-containing compounds, calculatedas elemental sulfur, less than about 10 ppm by weight of N-containingcompounds (calculated as elemental N), and less than about 10 ppm byweight of caustic, calculated as NaOH. Such low levels of base, sulfurand nitrogen impurities can be obtained by conventional techniques, asby the use of caustic to remove sulfur- and nitrogencompounds from arefinery C₄ stream, followed by water washing to remove caustic, dryingwith any of the above water absorbents, hydrogenating to remove C₄ -C₅diolefins (e.g., butadienes) (to a level of below 1 wt. %, preferably<1,000 ppm by weight) and cooling the resulting purified C₄ stream forfeed to the tubular reactors of the present invention, after admixingthe selected cocatalyst therewith.

The monomer feedstream is typically substantially free of aromaticcompounds, such as benzene, toluene, xylene, naphthalene and otheraromatic solvents (e.g., <10 ppm aromatic compounds) to avoid theresultant reactive degradation of the immobilized catalyst. Therefore,use of an aromatic solvent is not envisioned in this process.

It is contemplated that this process may be used to polymerize andcopolymerize various monomers from pure or mixed feedstreams such asisobutenes from pure or mixed streams (containing other butenes);n-butenes from streams containing small amounts of isobutenes (e.g.,less than about 5 wt. %); and sequentially isobutene from a mixedstream, and then n-butenes. It is also contemplated that this processmay be used to copolymerize various monomers including 1-butene,ethylene and hexane.

Other design parameters such as recycle rate and % diluents are mattersof choice in this instance and may be readily determined by one havingordinary skill in chemical engineering.

A material acting as a cocatalyst (or promoter) may optionally be addedto a monomer feedstock before that feed is introduced to a reactor or itmay be added separately to the reactor, e.g., to the catalyst bed. Avariety of conventional cocatalysts or equivalents can be used includingH₂ O, hydrogen halides, ROH and RX wherein X=halides and R=C₂ -C₂₄secondary or tertiary alkyl and the like. For example, gaseous,anhydrous HCl, may be employed as a cocatalyst. The HCl will be employedin a catalytically effective amount, which amount will generally rangefrom about 50 to 5,000 ppm by weight of the monomer feed, preferably 50to 500 ppm (e.g., 70 to 200 ppm) by weight of the monomer feed when themonomer feed comprises >5 wt. % isobutylene, and preferably from about100-5,000 ppm (e.g., 400-3,000 ppm) by weight when the feed comprisesn-butenes and <5 wt. % isobutylene. If anhydrous HCl is added to thefeedstream containing isobutene, t-butyl chloride is formed beforecontact with the solid catalyst. This has been found to promote thepolymerization of the isobutene. Water, in a catalytic amount, may beadded to the feedstock but is not preferred since it has a tendency tocause physical deterioration of the catalyst with time. Alcohols, suchas the preferred lower alkanols (e.g., methanol), may also be added. Ashas been pointed out above, the monomer feed is preferably anhydrous,and the reaction mixture is also preferably substantially anhydrous(that is, typically contains <50 ppm, more typically <30 ppm, and mostpreferably <10 ppm, by weight water based on the monomer feed).

The characteristics of the polymeric product of the present process willbe dependent upon the monomer feedstream, the particular immobilizedcatalyst, the optional cocatalysts, and the reaction conditions.Typically, Mn of the polymeric product will range from about 300 toabout 1,000,000, preferably 300 to about 500,000, more preferably about500 to about 100,000, and most preferably about 500 to about 25,000gm/mole. The molecular weight distribution (Mw/Mn) will typically rangefrom about 1.1 to about 8.0, more typically about 1.8 to about 3.0, andpreferably about 1.8 to about 2.5. The molecular weight of the polymerproduced according to the process of the present invention is inverselyproportional to the reaction temperature, and, surprisingly andunexpectedly, a relatively high molecular weight polymer can be producedat or near room temperature. In addition, all molecular weights ofpolymers can usually be produced at relatively lower temperatures byusing the immobilized catalysts of the present invention when comparedwith conventional carbocationic catalysts.

The product mixture may be withdrawn from the reactor and subsequentlytreated (e.g., by depressuring into a suitable gas/liquid separationdrum or other vessel) for separation of gaseous components therefrom(e.g., unreacted monomer such as isobutene, butene, butane, andisobutane). If desired, these separated gases can be compressed, cooledand recycled to the feed inlet to the tubular reactor, although the needfor such recycling is minimized or avoided by use of the process of thisinvention in view of the high olefin conversions which are obtainable. Aportion of the liquid reactor effluent can be recycled to the feed todilute the content of the monomers in the feed to the reactor, ifnecessary. Preferably, the monomers fed to the tubular reactor aresubstantially free of monomers recycled from the tubular reactoreffluent. Therefore, the monomer feedstream is preferably contacted withthe catalyst in the process of this invention on a once-through basis.

In addition to polymerization processes, the immobilized catalysts ofthe present invention may also be used in alkylation processes. As isknown in this art, alkylation may be simply described as the addition orinsertion of an alkyl group into a substrate molecule. Of particularinterest is the alkylation of aromatic, hydroxy aromatic, olefin, alkylhalide and alkane substrates and mixtures thereof. The hydroxy aromaticand aromatic compounds include, but are not limited to, toluene, xylene,benzene and phenol. Suitable alkylating agents include olefin, alkane,alkyl halide and mixtures thereof. The composition of each class ofalkylating agent is as described in conjunction with the correspondingsubstrate class of compounds subject to the proviso that the alkylatingagent class be different from the substrate class employed.

The hydroxy aromatic substrate compounds useful in the preparation ofthe alkylated materials of this invention include those compounds havingthe formula:

    Ar--(OH).sub.z

wherein Ar represents ##STR16## and z is an integer from 1 to 2, w is aninteger from 1-3, a is 1 or 2 and R_(a) =C₁ -C₂₄ alkyl.

Illustrative of such Ar groups are phenylene, biphenylene, naphthaleneand the like.

The aromatic substrate compounds useful in the preparation of thealkylated materials of this invention include those compounds having theformulas:

    Ar--R.sub.a and (Ar--R.sub.a).sub.w

wherein R is H or C₁ -C₂₄ alkyl and wherein Ar represents: ##STR17##wherein a is one or two and wherein R=C₁ -C₂₄ alkyl, C₃ -C₂₄ cyclic, C₆-C₁₈ aryl, C₇ -C₃₀ alkylaryl, OH, or H and w=1-3.

Illustrative of such Ar groups are benzene, phenylene, biphenylene,naphthalene, and anthrocene.

The alkane substrate which can be alkylated using the processes of thepresent invention include those having the formula C_(n) H_(2n+2)including but not limited to butane, ethane, propane, methane, hepane,heptane, octane, nonane, decane and the like.

The alkyl halide substrate will typically have the formula R⁸ Xr whereinR⁸ =C₁ -C₂₄ alkyl, C₃ -C₂₄ cyclic, C₆ -C₁₈ aryl, or C₇ -C₃₀ alkylaryland X=halide including Cl, F, Br and I, and r is a number from 0 to 4.Examples of alkyl halides include t-butyl chloride, ethyl chloride,n-butyl chloride and 1-chlorohexane.

The olefin substrate useful in the preparation of the alkylatedmaterials of this invention, and which may also be alkylated, are knownin the art and include those compounds having 2 to 200 carbon atoms. Theolefins may be monomers, oligomers or copolymers or polymers includingcopolymers. Nonlimiting examples which are illustrative of suchcompounds include ethylene, propylene, butene, C₂ -C₂₄ mono or diolefin,polybutene, poly-n-butene, polypropylene, low molecular weightpolyethylene, ethylene alpha-olefin copolymers, and combinations thereofand oligomers derived from C₂ -C₂₄ olefins.

The selected olefins, alkanes, alkyl halides, aromatic or hydroxyaromatic compound are contacted with a suitable alkylating agent in thepresence of a catalytically effective amount of at least one acidicalkylation catalyst under conditions effective to alkylate the substrateselected. The alkylation catalyst comprises the immobilized catalysts ofthe present invention. Also useful as catalysts are preformed complexes(or complexes formed in situ) of the immobilized catalyst with aromaticssuch as benzene, toluene and the like.

The substrate and alkylating agent will generally be contacted underreaction conditions, including mole ratio, temperature, time andcatalyst ratio sufficient to alkylate the substrate. The substrate willbe generally contacted in a molar ratio of from about 0.1 to 10,preferably from about 1 to 7, more preferably from about 2 to 5, molesof the substrate per mole of the alkylating agent. Conventional ratiosof alkylating agent will typically be used. The ratio will typically beabout 0.5 to 2:1, more typically about 0.8 to about 1.5:1, andpreferably about 0.9 to about 1.2:1. The selected catalyst can beemployed in widely varying concentrations. Generally, the catalyst willbe charged to provide at least about 0.001, preferably from about 0.01to 0.5, more preferably from about 0.1 to 0.3, moles of catalyst permole of substrate charged to the alkylation reaction zone. Use ofgreater than 1 mole of the catalyst per mole of substrate is notgenerally required. The reactants can be contacted with the immobilizedcatalyst emplying any conventional solid-liquid contacting techniques,such as by passing the reactants through the resin (e.g., in a catalystbed or through the resin (e.g., in a catalyst bed or through a membraneimpregnated or otherwise containing the catalyst or through a conduithaving deposited thereon a coating or layer of the catalyst) and theupper limit on the moles of catalyst employed per mole of substratecompound is not critical.

The temperature for alkylation can also vary widely, and will typicallyrange from about 20° to 250° C., preferably from about 30° to 150° C.,more preferably from about 50° to 80° C.

The alkylation reaction time can vary and will generally be from about 1to 5 hours, although longer or shorter times can also be employed. Thealkylation process can be practiced in a batchwise, continuous orsemicontinuous manner.

Alkylation processes of the above types are known and are described, forexample, in U.S. Pat. Nos. 3,539,633 and 3,649,229, the disclosures ofwhich are hereby incorporated by reference.

Generally, the % conversions obtained in the alkylation according to thepresent invention will be greater than about 50%, e.g., from 70 to 98%,and preferably from 80 to 95%, based on the percentage of the alkylatingagent charged which reacts. The precise conversion obtained will dependon the Mn of the substrate, e.g., polyalkene, the alkylationtemperature, reaction time and other factors, and conversions willgenerally decrease somewhat as polyalkene Mn increases. The alkylationprocess of this invention is particularly beneficial for olefins havingMn of from about 300 to 5,000, preferably 300 to 3,000.

It will be understood that when the alkylating agent is a polyalkene itcan be charged to the alkylation reaction zone alone or together with(e.g., in admixture with) other polyalkenes alkylating agents derivedfrom alkenes having from 1 to 20 carbon atoms (butene, pentene, octene,decene, dodecene, tetradodecene and the like) and homopolymers of C₃ toC₁₀, e.g., C₂ to C₅, monoolefins, and copolymers of C₂ to C₁₀, e.g., C₂to C₅, monoolefins, said additional polymer having a number averagemolecular weight of at least about 900, and a molecular weightdistribution of less than about 4.0, preferably less than about 3.0(e.g., from 1.2 to 2.8). Preferably such additional olefin polymerscomprise a major molar amount of C₂ to C₁₀, e.g., C₂ to C₅ monoolefin.Such olefins include ethylene, propylene, butylene, isobutylene,pentene, octene-1, styrene, etc. Exemplary of the additionally chargedhomopolymers are polypropylene, polyisobutylene, and poly-n-butene thelike as well as interpolymers of two or more of such olefins such ascopolymers of: ethylene and propylene; butylene and isobutylene;propylene and isobutylene; etc. Other copolymers include those in whicha minor molar amount of the copolymer monomers, e.g., 1 to 10 mole %, isa C₄ to C₁₈ non-conjugated diolefin, e.g., a copolymer of isobutyleneand butadiene: or a copolymer of ethylene, propylene and 1,4-hexadiene;etc. The additional such olefin polymers charged to the alkylationreaction will usually have number average molecular weights of at leastabout 900, more generally within the range of about 1,200 and about5,000, more usually between about 1,500 and about 4,000. Particularlyuseful such additional olefin alkylating agent polymers have numberaverage molecular weights within the range of about 1,500 and about3,000 with approximately one double bond per chain. An especially usefuladditional such polymer is polyisobutylene. Preferred are mixtures ofsuch polyisobutylene with ethylene-propylene copolymers wherein at least30 wt. % of the copolymer chains contain terminal ethenylenemonounsaturation as described above.

The number average molecular weight for such polymers can be determinedby several known techniques. A convenient method for such determinationis by gel permeation chromatography (GPC) which additionally providesmolecular ,weight distribution information; see W. W. Yau, J. J.Kirkland and D. D. Bly, "Modern Size Exclusion Liquid Chromatography",John Wiley and Sons, New York, 1979.

As previously mentioned, the immobilized catalysts and processes of thepresent invention offer a number of advantages over conventionalcarbocationic catalysts and polymerization processes.

A particularly significant advantage of the immobilized catalyst andprocess of the present invention is that the catalyst is usable forprolonged periods of time before regeneration is required resulting insignificant cost savings, as well as the elimination of significantamounts of hazardous waste typically generated in conventional LewisAcid processes.

Another surprising and unexpected advantage of the present invention isthat the polymerization process can be operated, depending upon thedesired molecular weight of the polymer, at relatively highertemperatures, even ambient temperatures.

Yet another surprising and unexpected advantage of the present inventionis that gaseous catalysts such as BF₃ can now be immobilized.

Another advantage of the immobilized catalysts of the present inventionis that the catalysts are easy to dispose of in an environmentallyadvantageous manner.

Yet still another advantage of the immobilized catalysts of the presentinvention is that the catalysts can be regenerated in situ, for example,by first using an acid wash followed by Lewis Acid reagent.

Another advantage of the immobilized Lewis Acid catalysts of the presentinvention is that they can be used in most organic solvents. Theimmobilized catalysts do not require that their use be limited tospecific solvents, for example, halogenated solvents.

And yet another advantage of the immobilized Lewis Acid catalysts of thepresent invention is that the polymers produced using these catalystshave little or no catalyst residue.

Polybutenes and other polymers and copolymers in the molecular weightrange of 500 to 20,000 prepared in accordance with the process of thepresent invention are particularly useful as a feedstock for theproduction of improved lubricating oil dispersants. These dispersantsgenerally comprise the reaction product of polybutenyl (Mn of 700 to10,000) succinic anhydride, or the acid form thereof, with monoamines orpolyamines having at least one primary or secondary amino group such asthe alkylene polyamines, particularly the ethylene polyamines, thepolyoxyalkylene amines, aromatic and cycloaliphatic amines,hydroxyamines, monoaliphatic and dialiphatic substituted amines. Usefuldispersants are also formed by reacting monohydric and polyhydricalcohols with the polyisobutenyl succinic anhydride or diacid providedin accordance with this invention and preferred materials are thusderived from polyols having 2 to 6 OH groups containing up to about 20carbon atoms such as the alkene polyols and alkylene glycols. Alsosuitable are the polyoxyalkylene alcohols such as polyoxyethylenealcohols and polyoxypropylene alcohols, monohydric and polyhydricphenols and naphthols, ether alcohols and amino alcohols and the like.Borated derivatives of the foregoing dispersants are also useful,especially borated nitrogen containing dispersants resulting fromboration with boron oxide, boron halide, boron acids and esters toprovide 0.2 to 2.0 weight percent boron in the dispersant. Metals andmetal-containing compounds can also form useful dispersants and theseare compounds capable of forming salts with the polybutenyl succinicanhydride or acid (using the polybutenes of the present invention) Theseinclude metals such as the alkali metals, alkaline-earth metals, zinc,cadmium, lead, cobalt, nickel, copper, molybdenum, in the form ofoxides, carboxylates, halides, phosphates, sulfates, carbonates,hydroxides and the like.

Lubricating oil compositions will usually contain dispersants in amountsof from about 1 to 15 weight percent based on the overall weight of thecomposition. Lubricating oil compositions will typically contain otheradditives in customary amounts to provide their normal attendantfunctions such as metal detergents or basic metal detergents, antiwearadditives, antioxidants, viscosity modifiers and the like. Dispersantsare conventionally packaged and dispensed in the form of solutionconcentrates containing about 20 to 50 wt. % dispersant in a mineraloil.

The following examples are illustrative of the principles and practiceof this invention, although not limited thereto. Parts and percentageswhere used are parts and percentages by weight. The structure of thecatalysts where used in the examples are only meant to serve to identifythe particular immobilized catalyst and do not represent the actualstructure of the catalyst.

EXAMPLE 1 (a) Copolymerization of Propylene and Hexenyl-9-BBN

Into a 500 ml evacuated flask containing 200 ml of toluene, 4 ml ofpropylene (50 mmol) was introduced at a temperature of -78° C. The flaskwas sealed and gradually warmed to room temperature to dissolve the gas.In a dry box, 4 g (20 mmol) of hexenyl-9BBN were added followed by asuspension of 0.168 g (1,113 mmol) TiCl₃ AA ("AA" is alumina activated)and 0.754 g (6.604 mmol) Al(Et)₃ aged for 1/2 hour in 30 ml of toluene.Almost immediately, a precipitate could be seen in the deep purplesuspension. The reaction was terminated after 1/2 hour by addition ofisopropanol. A white, rubbery polymer was precipitated and thenrepeatedly washed with more isopropanol. The white rubbery polymer wassqueeze dried and then further dried in a vacuum chamber to yield 3.5 gof borane-containing polypropylene.

(b) Synthesis of Poly(propylene-co-1-hexenyl-6-ol)

0.674 g of the borane-containing polypropylene copolymer of Part (a) wasplaced in 75 ml of THF in a 250 ml stirred round bottom flask fittedwith an airtight septum to form a cloudy white suspension. The stirredsuspension was cooled to 0° C. in an ice bath before the addition viasyringe of 2 molar equivalents (based on alkylborane content) ofdegassed NAOH solution followed by dropwise addition of 3 equivalents of30% H₂ O₂ solution. The flask was gradually warmed to 55° C. and held atthat temperature for 4 hours. The functionalized copolymer wasprecipitated with water, washed with acetone, refluxed in MeOH(methanol), and again precipitated with water and washed with acetone.

EXAMPLE 2 (a) Preparation of Immobilized Catalysts

In a dry 200 ml flask, equipped with a magnetic stirring bar and aconnecting tube leading to a nitrogen source, the functionalizedcopolymer (2 g) of Example 1 was suspended in 50 ml of CH₂ Cl₂ with 180mg of triethyl aluminum (AlEt₃) for 2 hours at ambient temperature. Thecomposition of the copolymer included 98 mole % of propylene and 2 mole% of hexenol. The melting point of this polymer was about 165° C. Thesolid particles were separated from solution by syringing out the liquidportion and then were washed with dry and oxygen-free CH₂ Cl₂ severaltimes. The resulting immobilized catalyst (PP--O--AlEt₂) was dried for24 hours, at room temperature and 10 μm Hg pressure, before transferringinto a dry box. For convenience, the following short hand designation ofPP--O--AlEt₂ is used with PP being the unfunctionalized polymeric units,i.e. polypropylene, and --O--AlEt₂ indicating the immobilized catalyststructure, i.e. - 1-hexenyl-6-0-diethyl aluminum.

(b) Polymerization of Isobutylene

A polymerization was carried out in a high vacuum apparatus consistingof two 200 ml flasks equipped with magnetic stirrers (FIG. 7). Onestopcock 30 was used to separate two flasks (A and B), the otherstopcock 40 located on the top of flask A was used to control the vacuumcondition and inert gas flow. After the apparatus was dried for over 12hours, a portion of the immobilized catalyst PP--O--AlEt₂ (0.2 g) ofpart (a) was charged to flask B in a dry box condition. The system wasconnected to a vacuum line and pumped to high vacuum, and then 50 ml dryCH₂ Cl₂ and 2 ml (1.2 g) dry isobutene were vacuum-distilled into flaskA by immersing the flask in a dry ice/acetone bath. The catalyst tomonomer molar ratio was 1/200. After controlling both flasks at 0° C.,the monomer solution in flask A was poured into flask B. Thepolymerization occurred at 0° C. with stirring. After a half hourreaction time, the catalyst was allowed to settle. The solution portion,polyisobutylene, CH₂ Cl₂ and unreacted isobutene, was then carefullypoured back into flask A without disturbing the precipitate (immobilizedcatalyst). The precipitate was further washed by low temperaturedistillation of pure CH₂ Cl₂ from flask A. This procedure was repeatedseveral times to ensure complete removal of polyisobutylene from thesurface of the immobilized catalyst. The product was then decanted fromflask A. Evaporation under vacuum gave 1.2 g (100% yield) of viscouspolymer. A GPC study of resulting polymer showed a relatively highmolecular weight (Mn=24,516 and Mw=160,062).

A repeat polymerization using the recovered catalyst and the samereaction condition gave about 1.05 g (87% yield) polyisobutylene. Thepolymer had slightly lower average molecular weight (Mn 14,325 andMw=120,111). A third cycle polymerization resulted in polymer with about70% yield and similar number average molecular weight, weight averagemolecular weight and molecular weight distribution.

EXAMPLE 3

The immobilized catalyst of Example 2 (a) was used to polymerizeisobutene in hexane solvent. The polynerization was carried out usingthe reaction procedure of Example 2 (b), using 0.2 g of PP--O--AlEt₂ and1.2 g of isobutene in 50 ml of dry hexane. The polymerizationtemperature was at OOC. The product was a water white, very viscouspolymer with almost 100% yield and moderate molecular weight (Mn 5,667and =22,496). This immobilized catalyst was reused for a Mw second batchpolymerization to generate an 80% yield with a reproducible molecularweight (Mn 6,330 and Mw=21,898).

EXAMPLE 4

Following the procedure of Example 2 (a), hydroxy functionalizedpolypropylene copolymer (i.e. poly(propylene-co-1-liexenyl-6-ol)) wasreacted with excess AlCl₃ in CH₂ Cl₂ solution. Due to the limitedsolubility of AlCl₃, the contact time was about 24 hours at roomtemperature. This reaction evolved HCl and produced PP--O--AlCl₂catalyst which was then washed free of unreacted AlCl₃ and HCl beforedrying under vacuum overnight, where PP--O--AlCl₂ is analogous to theshort hand as described in Example 2 (a).

This catalyst was used in the polymerization of isobutene using theprocedure of Example 2(b). The solvent was CH₂ Cl₂ and the reactiontemperature was 30° C. Within one half hour polymerization time, almost100% yield of polyisobutylene was obtained with a very broad molecularweight distribution (Mn 15,334 and=369,495). The second cycle wasoperated at 0° C. The yield was reduced to 55% with a similar broadmolecular weight distribution and a relatively lower molecular weight(Mn=4,657 and Mw=130,843).

EXAMPLE 5

Hydroxy group functionalized polypropylene copolymer(poly(propylene-co-1-hexenyl-6-ol)) (0.2 g) suspended in 100 ml of CH₂Cl₂ solution was contacted with BF₃ by condensing BF₃ (excess) into thesolution. The reaction mixture was stirred for 6 hours before pumpingout the unreacted BF₃, HF and CH₂ Cl₂ solvent. Under high vacuum (<5 um)for overnight, the catalyst was contacted with monomer solution (1. 2 gof isobutene in 50 ml of hexane) using the technique of Example 2 (b) Aviscous polymer was obtained with an overall yield of about 75%.

EXAMPLES 6-15

Cationic polymerizations were carried out in accordance with theprocedure of Example 2(b); however, the immobilized catalyst used wasPP--O--AlEtCl. This was derived from the Lewis Acid aluminum ethyldichloride (AlEtCl₂). PDI is the polydispersity index which is Mw/Mn.This is the same as molecular weight distribution. A narrow molecularweight distribution, i.e. , low PDI, is desirable for use of the polymeras a dispersion agent. The results are presented in the following table.

                  TABLE 1                                                         ______________________________________                                                    Temp    Time                Yield                                 Solvent     (°C.)                                                                          (Hr)     --Mn PDI   (%)                                   ______________________________________                                        Ex. 6  hexane   -10     2     9,500 2.7   35                                  Ex. 7  hexane   -10     4     10,200                                                                              3.1   55                                  Ex. 8  hexane    0      4     4,050 3.9   65                                  Ex. 9  hexane    0      6     4,700 3.2   80                                  Ex. 10 hexane   25      4     2,100 3.7   70                                  Ex. 11 hexane   25      6     1,750 3.8   90                                  Ex. 12 hexane   25      8     1,850 3.6   100                                 Ex. 13 CH.sub.2 Cl.sub.2                                                                       0      2     15,300                                                                              3.4   65                                  Ex. 14 CH.sub.2 Cl.sub.2                                                                       0      4     14,700                                                                              3.1   85                                  Ex. 15 CH.sub.2 Cl.sub.2                                                                       0      6     13,500                                                                              2.8   95                                  ______________________________________                                    

EXAMPLES 16-21 (a) Preparation of Supported Catalysts PB--O--AlCL₂

In the following Examples, the supporting material was hydroxyfunctionalized polybutene-1 copolymer (poly(butene-1-co-1-hexenyl-6-ol))which contained 10 mole % of 1-hexenyl-6-ol (hydroxyl groups). Thepolymer was ground to a fine powder form having high surface area byfreezing with liquid nitrogen and then pulverizing by placing in asealed metal container with a metal ball and shaking the container andits contents for a sufficient length of time to pulverize theimmobilized catalyst such that the average particle size was about 0.1mm and the particles ranged in size from about 0.01 mm to about 0.5 mm.In a dry 200 ml flask, the hydroxyl functionalized polybutene copolymer(0.2 g) was suspended in 50 ml of toluene solution with 10 mole % excessethyl aluminum dichloride (EtAlCl₂) for 5 hours at 25° C. The powderswere separated from solution by filtration through glass fret, and thenwere washed with dry and oxygen-free toluene for several times. Afterdrying, the resulting immobilized catalyst (PB--O--AlCl.sub. 2) wassubjected to the structural characterization. Elementary analysis and ²³Al NMR confirmed the complete conversion of --OH to --OAlCl₂ groups.

(b) Polymerization of Isobutylene

A polymerization of isobutylene by PB--O--AlCl₂ was carried out in ahigh vacuum apparatus as described in Example 2. PB--O--AlCl₂ (50 mg)was charged to flask B in a dry box condition. The system was connectedto a vacuum line and pumped to high vacuum, 50 ml dry hexane and 4 ml(2.4 g) dry isobutylene were vacuum-distilled into flask A by immersingthe flask in a dry ice/aceton bath. The monomer solution in flask A waswarmed up to room temperature before pouring into flask B. Thepolymerization occurred at ambient temperature with stirring. After 20minutes reaction time, the catalyst was allowed to settle. The solutionportion, polyisobutylene/hexane, was then carefully pipetted our fromflask B without disturbing the precipitate (immobilized catalyst). Aftersolvent-evaporation under vacuum, a viscous polyisobutylene polymer wasobtained. This procedure was repeated for several times to evaluate thepolymerization reactivity in the subsequent cycles. The results aresummarized in the following Table 2.

                  TABLE 2                                                         ______________________________________                                        Reaction                Temp.                                                 Time (Min.)    Yield    (°C.)                                                                           Mn    PDI                                    ______________________________________                                        Ex. 16 20          100%     25     1067  2.02                                 Ex. 17 20          100%     25     1157  1.61                                 Ex. 18 20          100%     25     1135  1.75                                 Ex. 19 10          100%     25     1120  1.68                                 Ex. 20 40          100%      0     4228  2.37                                 Ex. 21 30          100%      0     4526  2.34                                 ______________________________________                                         ##STR18##                                                                

EXAMPLES 22-31 Polymerization of Isobutylene by Immobilized CatalystsPB--O--AlCl₂

As in Examples 16-21, the same functionalized polybutene-1 copolymerwith 10 mole % of 1-hexenyl-6-ol (hydroxyl groups) was used in thepreparation of polyisobutylene. The major difference was the form offunctionalized polymer. A piece of hydroxylated polybutene solid (0.1 g)was reacted with EtAlC₂ overnight at 25° C. The reaction was completedespite the inhomogeneity of reaction conditions. Elementary analysisshowed the Ratio of Al:O:Cl equal to 1:1:2. This indicated that thereaction was occurring at the ethyl site. The polymerization ofisobutylene by PB--O--AlCl₂ particles was carried out in a high vacuumapparatus as described before. In each reaction cycle, 4 ml (2.4 g) ofdry isobutylene were used. The results are summarized in Table 3, withRT at about 25° C.

                                      TABLE 3                                     __________________________________________________________________________                          Time                                                                              Yield                                               Catalyst    Solvent                                                                            Temp (hr)                                                                              (%)  --Mn                                                                              PDI                                        __________________________________________________________________________    Ex. 22                                                                            PB--O--AlCl.sub.2                                                                     Hexane                                                                             RT   2   100 1,375                                                                              3.03                                       Ex. 23                                                                            PB--O--AlCl.sub.2                                                                     Hexane                                                                             RT   20  100 1,964                                                                              2.59                                       Ex. 24                                                                            PB--O--AlCl.sub.2                                                                     Hexane                                                                             RT   20  100 1,316                                                                              2.41                                       Ex. 25                                                                            PB--O--AlCl.sub.2                                                                     Hexane                                                                             RT   5   100 1,014                                                                              2.15                                       Ex. 26                                                                            PB--O--AlCl.sub.2                                                                     Hexane                                                                             RT   3    90 1,398                                                                              2.38                                       Ex. 27                                                                            PB--O--AlCl.sub.2                                                                     Hexane                                                                             RT   1    45 1,237                                                                              2.36                                       Ex. 28                                                                            PB--O--AlCl.sub.2                                                                     Hexane                                                                             RT   5   100 1,125                                                                              2.41                                       Ex. 29                                                                            PB--O--AlCl.sub.2                                                                     Hexane                                                                             0°C.                                                                        6    70 5,454                                                                              2.63                                       Ex. 30                                                                            PB--O--AlCl.sub.2                                                                     CH.sub.2 Cl.sub.2                                                                  -30° C.                                                                     1   100 180,976                                                                            4.12                                       Ex. 31                                                                            PB--O--AlCl.sub.2                                                                     CH.sub.2 Cl.sub.2                                                                  0° C.                                                                       1    95 100,253                                                                            8.6                                        __________________________________________________________________________

EXAMPLES 32-34 Polymerization of Isobutylene

A piece of hydroxylated polybutene-1 copolymer solid (0.1 g) as inExamples 16-21 (i.e. poly(butene-1-col-hexenyl-6-ol)) was reacted withBF₃ which was condensed in CH₂ Cl₂ solution. The reaction took place for2 hours at 25° C. before distillating out excess BF₃ and CH₂ Cl₂ Theresulting immobilized catalyst was used in the polymerization ofisobutylene. Similar reaction procedures were followed in the evaluationof the immobilized catalyst. The results are summarized in the followingTable 4. The reaction of the BF₃ with the hydroxylated polybutene-1copolymer resulted in the formation of a complex wherein the BF₃ iscomplexed with the hydroxyl groups in the copolymer via a pi (π) bond.

                                      TABLE 4                                     __________________________________________________________________________                           Time                                                                              Yield                                              Catalyst     Solvent                                                                            Temp (hr)                                                                              (%)  --Mn                                                                             PDI                                        __________________________________________________________________________    Ex. 32                                                                             PB--OH--BF.sub.3                                                                      Hexane                                                                             RT   5   95  400 1.1                                        Ex. 33                                                                             PB--OH--BF.sub.3                                                                      Hexane                                                                             RT   12  98  445 1.2                                        Ex. 34                                                                             PB--OH--BF.sub.3                                                                      Hexane                                                                             0°C.                                                                        4   95  576 1.2                                        Ex. 35                                                                             PB--OH--BF.sub.3                                                                      Hexane                                                                             -15° C.                                                                     4   50  662  1.72                                      __________________________________________________________________________

EXAMPLES 36-46 Polymerization of Isobutylene by a Mixture ofPB--O--AlEtCl and (PB--O)₂ --AlCl

A piece of the hydroxylated polybutene-1 copolymer solid (0.1 g) ofExamples 17-22 was reacted with Et₂ AlCl overnight at 25° C. Thereaction was complete, resulting in a mixture of PB--O--AlEtCl and(PB--O)₂ --AlCl. This mixed, solid particle, immobilized catalyst wasused in the polymerization of isobutylene. The reaction conditions ofExamples 16-21 were used to evaluate the reactivity of the immobilizedcatalyst. The reaction time was about 5 hours. The results aresummarized in the following Table 5.

                  TABLE 5                                                         ______________________________________                                                    Temp.                     Yield                                   Solvent     (°C.)                                                                           Mn       Mw      (%.)                                    ______________________________________                                        Ex. 36 Hexane   -10      9,525  25,254  100                                   Ex. 37 Hexane   0        4,037  16,267   95                                   Ex. 38 Hexane   0        4,705  15,454   90                                   Ex. 39 Hexane   25       2,103   7,803   95                                   Ex. 40 Hexane   25       2,038   7,408   82                                   Ex. 41 Hexane   25       1,740   6,540  100                                   Ex. 42 Hexane   25       1,844   6,763  100                                   Ex. 43 CH.sub.2 Cl.sub.2                                                                      0        24,516 90,064  100                                   Ex. 44 CH.sub.2 Cl.sub.2                                                                      0        12,575 100,235 >80                                   Ex. 45 CH.sub.2 Cl.sub.2                                                                      -30      45,334 180,976 100                                   Ex. 46 CH.sub.2 Cl.sub.2                                                                      0        8,945  100,253  95                                   ______________________________________                                    

EXAMPLE 47

The immobilized catalyst of Examples 6-15 is used to make a coatingcomposition. The coating composition is made by mixing 5 wt. % parts ofthe catalyst with 95 wt. % trichlorobenzene in a conventional mixingvessel at room temperature for a sufficient amount of time to completelydissolve the immobilized catalyst.

The composition is coated onto the interior surface of a 316-stainlesssteel reactor vessel. The coating is applied using a conventionalspraying apparatus. After application, the coating is dried by heatingat 150° C. under vacuum until dry. The coating is uniform and has anaverage thickness of about 0.1 mm. The coated reactor may be used in aPolymerization process to polymerize monomer feeds.

EXAMPLE 48

The immobilized catalyst of Examples 6-15 is fed to a conventionalinjection molding apparatus having a feed means, heating means, coolingmeans, extruding means and molds. The catalyst is heated undersufficient heat and pressure to a temperature of at least about 185° C.,injected into the mold and molded under sufficient heat and pressure,and for a sufficient time, to form an object having the shape of acolumn packing ring. The object is then cooled and removed from themold. The object may be used in a packed column reactor vessel topolymerize monomer feeds.

EXAMPLE 49

The immobilized catalyst of Examples 6-15 is placed into a conventionalvessel having a heating jacket and heated to a temperature of about 200°C. for a sufficient amount of time to liquify the immobilized catalyst.Ceramic spheres having a diameter of about 1 mm are dipped into theliquid immobilized catalyst and removed. The spheres have a liquidcoating of the immobilized catalyst which solidifies upon cooling. Thecoated spheres are used as catalyst in a batch reactor in apolymerization process.

EXAMPLE 50

The immobilized BF₃ of Examples 33-36 is charged to a conventionalstirred tank reactor having heating and cooling means and agitatingmeans. An excess molar ratio of an aromatic hydrocarbon (benzene) ischarged to the reactor. A polyalkene (poly-n-butene (PNB)) is fed to thereactor. The PNB reacts with the benzene under suitable reactionconditions at a sufficient temperature (40° C.) and pressure, and for asufficient time, effective to alkylate the aromatic hydrocarbon. Theresulting product PNB alkylated benzene, is then discharged from thereactor and separated from unreacted benzene by distillation.

EXAMPLE 51

The process of Example 50 is repeated except that the immobilizedcatalyst is the immobilized catalyst of Example 22-31. The aromatichydrocarbon is benzene and the alkylating olefin is propylene oligomerwith an average molecular weight of about 340. The reaction temperatureis about 30° C. and the reactor is a continuous stirred tank reactor.

EXAMPLE 52

A continuous tubular reactor is packed with the immobilized catalyst ofExamples 16-21. Isobutane is fed into the reactor in a feedstream and,simultaneously, isobutylene from a refinery feedstream is fed into thereactor. A cocatalyst, HCl, is also fed into the reactor. The mixture isheld in the reactor for a sufficient length of time and under sufficienttemperature and pressure to alkylate the butane to a degree of about50%. Branched octane (alkylated butane) and the unreacted monomers arewithdrawn in a discharge stream. The branched octane is separated fromthe unreacted monomers by distillation.

EXAMPLE 53

The functionalized copolymer of Examples 16-21 is reacted with n-butyllithium to form an intermediate salt in the following manner. To aconventional reactor vessel having a mixing means, is charged hexane andthe functionalized copolymer of Example 1. The functionalized copolymeris dispersed in the hexane by mixing. Then, an excess (1.1-5 times molarratio) of n-butyl lithium hexane solution (1.5 m) is added to thevessel. The reaction is held at room temperature (about 25° C.) for twohours. Then, the resulting intermediate (functionalized copolymer salt)is removed by filtration and washing with pure hexane. The resultingintermediate is then reacted with BF3 utilizing the procedure ofExamples 32-35 to form a catalyst having a structure identified asPB--O--BF₂ wherein the BF₃ is chemically reacted with, and chemicallybonded to, the functionalized thermoplastic copolymer. Similar reactionconditions are followed in the evaluation of the catalyst usingisobutylene monomer as a feed. The resulting polymers are observed tohave an Mn in the range of about 1,000 to about 1,500.

EXAMPLES 54-57

Functionalization chemistry, as recited in Chung, T. C.; Macromolecules,1988, 21, 865, Ramakrishnan, S.; Berluche, E.; Chung, T. C.;Macromolecules, 1990, 23, 378, Chung, T. C.; Rhubright, D.,Macromolecules, 1991, 24, 970, using a borane monomer as the comonomerin the polymerization of polyolefins by Ziegler-Natta catalyst, was usedto prepare a polyolefin structure. Isotactic polypropylene, as recitedin Chung, T. C.; Rhubright, D., Macromolecules, 1991, 24, 970, with 5mole % of hydroxy groups and isotactic polybutene (PB--OH) with 12 mole% of hydroxy groups, were used as the substrates to immobilize Lewisacids which are active in the carbocationic polymerization ofisobutylene. Both functionalized polyolefins have "brush-like"microstructures, as recited in Chung, T. C., Chem. Tech. 27, 496, 1991.

FIG. 1 shows the PP--OH product having crystalline phase and functionalgroups selected from --OH, --I, AIX₂ and BX₂ wherein X is a halide oralkylhalide.

Several experiments were introduced in which the hydroxylatedpolyolefins, polypropylene or polybutene, were reacted with Lewis acids,such as EtAlCl₂, Et₂ AlCl and BF₃ according to the following equation:##STR19## P is the partially crystalline polyolefins which have 5 or 12mole % of hydroxy groups. M is B or Al atom, the ligands (a, b, c) canbe either alkyl or halogen groups and x, y can be a, b, c or oxygen. Thehydroxy groups react with either alkyl group or halogen. Additionally,two hydroxy groups can react with one M. The reaction was usuallycarried out at room temperature by stirring the hydroxylated polymerwith excess Lewis acid solution for a few hours. The unreacted reagentwas removed by washing the resulting immobilized catalyst with puresolvent for several times. In general, the alkyl groups have been foundto be more reactive to hydroxy group than halides. To enhance thereactivity in BF₃ case, the hydroxy groups in polymer were usuallymetalated, such as by the reaction with alkyl lithium, beforeimmobilization reaction.

Solid state ²⁷ Al and ¹¹ B NMR measurements were used to analyze thecatalytic species in the immobilized catalyst. Three immobilizedcatalysts were studied in detail, by comparing the immobilized catalystswith their corresponding soluble ones. FIG. 4 shows the ²⁷ Al spectrumof the catalyst (A), prepared by reacting hydroxylated polypropylenewith EtAlCl₂ at room temperature. Only a singlet peak at 89 ppm,corresponding to --OAlCl₂ with four coordinations, as recited in Benn,R.; Rufinska, A., Angew. Chem. Int. Ed. Engl., 1986, 25, 861, wasobserved with the absence of 170 ppm, corresponding to EtAlCl₂. It wassurprising to find such a selective reaction, the alkyl-aluminum bond ismuch more reactive than aluminum-halide bond in the reaction withalcohol.

The same chemical reaction was also observed in the reference sample,using 1-pentanol, instead of the hydroxylated polypropylene, in thereaction of EtAlCl₂ under the similar reaction condition. FIG. 4A is thesolution ²⁷ Al NMR spectrum of resulting C₅ --OAlCl₂, which indicatesthe same chemical shift, corresponding to single --OAlCl₂ species. Theelemental analysis study, with the same theoretical and experimentalmole ratio of elements in C₅ --OAlCl₂ compound, also reconfirms theresult.

The immobilization reaction was substantially complete in relativelymild reaction condition. Most of hydroxy groups disappeared despite theshape and size of hydroxylated polymer particles. The elemental analysisresults show that the concentration of Al species in the immobilizedcatalyst was very close to that of hydroxy group in the originalfunctionalized polyolefin. The complete reaction in this heterogeneoussystem supports the morphologic arrangement in FIG. 1, most of hydroxygroups are located in the amorphous phase which can be easily reached byEtAlCl₂ reagent.

In the case of Et₂ AlCl, there are two alkyl groups which are veryreactive to hydroxy group. Using excess Et₂ AlCl reagent to the hydroxygroups (12%) in PB--OH, it was expected that the resulting immobilizedcatalyst (B) would be a mixture. FIG. 5 compares the solid state ²⁷ AlNMR spectrum of the immobilized catalyst (B) to the solution ²⁷ Al NMRspectrum of the corresponding small molecule by reacting 1-pentanol withthe stoichemetric amount of Et₂ AlCl (FIG. 5A). Both show similarresults with three main peaks at about 93, 37, 4 ppm, corresponding to--OAlEtAl (four coordinations), --O)₂ AlEt (five coordinations) and--O)₂ AlCl (six coordinations) respectively, as recited in Benn, R.;Rufinska, A., Angew. Chem. Int. Ed. Engl., 1986, 25, 861, and no peak at170 ppm, corresponding to Et₂ AlCl.

The relative peak intensity between three Al peaks was also very similarin both spectra. The same degree of the reaction to form various speciesseems to indicate that the availability of hydroxy groups in polybutenesolid is very close to that of soluble 1-pentanol case. This result isalso consistent to the morphologic structure of "Brush-like"hydroxylated polybutene (FIG. 1).

Catalyst (C) is an immobilized BF₃ catalyst. The reaction between BF₃and hydroxylated polymers (PB--OH) was conducted in two ways. The directreaction between BF₃ and hydroxy group is very slow, and possibly formsthe BF₃ /OH complexes. The more effective immobilization reaction wascarried out by using alkoxide groups. The metallization reaction ofhydroxy groups was done by simple mixing of the polymer particles withbutyl lithium solution. After washing out the excess butyl lithium, thepolymer particles were subjected to BF₃ /CH₂ Cl₂ solution. The similarprocedure was done in the control experiment, using 1-pentanol smallmolecule. FIGS. 6 and 6A compares their ¹¹ B NMR spectra. Both spectraare almost identical with a peak at about 0 ppm, corresponding to --OBF₂group, as recited in Noth, H.; Wrackmeyer, B.; Nuclear MagneticResonance Spectroscopy of Boron Compounds; Springer-Verlag, 1978. Thisresult was also reconfirmed by elemental analysis study, it shows themole ratio of 1:2 between B and F elements in PB--OBF₂ sample.

Materials and Measurements

In Examples 54-57 the following chemicals, 9-borobicyclononane (9-BBN),Al(Et)₃, AlEtCl₂, Al(Et)₂ Cl and BF₃ (Aldrich), and TiCl₃ AA (Stauffer),were used as received. HPLC grade toluene and THF were distilled fromsodium anthracide. Isopropanol and 1,5-hexadiene were dried with CaH₂and distilled under N₂. Propylene (Matheson) was passed through P₂ O₅and NaOH columns before drying with Al(Et)₃ at low temperature.Isobutylene (Matheson) was used without further purification. All themanipulations were carried out in an innert atmosphere glove box or on aSclenck line.

The molecular weight of polyisobutylene was determined using Waters GPC.The columns used were of Phenomenex Phenogel of 10⁴, 10³, 500 and 100 A.A flow rate of 0.7 ml/min was used and the mobile phase was THF. Narrowmolecular weight polystyrene samples were used as standards. All of thesolution NMR's were done on Bruker AM 300 machine. In ²⁷ Al NMR studies,toluene was used as solvent with deuterated toluene as lock solvent. For¹ H NMR studies, deuterated chloroform was used as solvent. MAS ²⁷ AlNMR were conducted at CSU NMR Center on a Bruker AM 600 NMR spectrometer(²⁷ Al resonance frequency of 156.4 MHz and 14.5 KHz MAS speed). MAS ¹¹B NMR were conducted on Chemagnetics CMX 300 NMR spectrometer (¹¹ Bresonance frequency of 95.4 MHz and 4 KHz MAS speed).

Preparation of Hydroxylated Polyolefins

In a typical case, 1.9 ml of propylene at approximately 78° C. (0.0293moles) was transferred into a 500 ml evacuated flask containing 150 mlof toluene. The flask was sealed and gradually warmed to roomtemperature to dissolve the gas. In a dry box; 11,987 g (0.0587 mole) ofhexenyl 9-BBN were added followed by a suspension of 0.168 g(1.113×10⁻³) TiCl₃ AA and 0.754 g (6.604×10⁻³ mole) Al(Et)₃ aged for 1/2hour in 30 ml of toluene. Almost immediately precipitate could be seenin the deep purple suspension. The reaction was terminated after 1/2hour by addition of isopropanol. The polymer was precipitated and thenrepeatedly washed with more isopropanol. Borane containing polypropylene(0.674 g) was placed in 75 ml of THF in a 250 ml roundbottom fitted withan air-tight septum to form a cloudy white suspension. The stirringsuspension was cooled to 0° C. in ice bath before the addition viasyringe of 2 molar equivalents (based on alkylborane content) ofdegrassed NaOH solution followed by dropwise addition of 3 equivalentsof 30% H₂ O₂ solution. The flask was gradually warmed to 55° C. and heldat that temperature for 4 hours. The polymer was precipitated withwater, washed with acetone, refluxed in MeOH, and precipitated withwater and again washed with acetone.

Immobilization of Aluminum Compounds (EtAlCl₂ and Et₂ AlCl)

Two hydroxylated polymers, polypropylene containing 5 mole % hydroxygroups and polybutene containing 12 mole % hydroxy groups were used inthe preparation of immobilized catalysts. Both polymers were slightlyswellable in toluene. The reactions with the aluminum reagents werecarried out at room temperature under the inert atmosphere.

Both fine powder and big chunk polyolefin particles were treated in thesame way. In a typical example, the hydroxylated polyolefin (150 mg)polymer, suspended in toluene (15 ml), was mixed with excess aluminumcompounds (approximately 10 mmole). After a reaction time for 3 hours,polyolefin was filtered and washed with hexane repeatedly to removeremaining aluminum compounds. Based on the elemental analysis and ²⁷ AlNMR studies, most of hydroxy groups were reacted without any unreactedaluminum compound in the polymer.

Synthesis of C₅ --O--AlCl₂

In a control reaction, pentanol (0.5 ml, 4.6 mmole) dissolved in 5 mltoluene was reacted with 0.48 ml (4.6 mmole) EtAlCl₂ which was dilutedwith 5 ml toluene. The solution of EtAlCl₂ was cooled to approximately78° C. and to this cooled solution pentanol solution was added dropwise.It was stirred at approximately 78° C. for 15 minutes and then warmed upto room temperature. Toluene was removed under vacuum.

Immobilization of Boron Trifluoride

In the reaction with BF₃, polyolefin containing hydroxy groups (150 mg)was reacted with a saturated solution of dichloromethane (15 ml) withboron trifluoride for 12 hours. The excess boron trifluoride anddichloromethane was removed under vacuum. The most effective methodinvolved a pretreatment of hydroxylated polyolefin (150 mg) with 0.1 ml(1 mmole) of n-BuLi (10M) in 7 ml of toluene for 1 hours. Polyolefin wasfiltered and washed with hexane to remove excess lithium compounds. Thetraces of solvent from polyolefin powder were removed by vacuum. To thispolymer a saturated solution of dichloromethane with BF₃ was added. Thismixture was stirred at room temperature for 3 hours. Dichloromethane andexcess BF₃ were removed on vacuum line.

Synthesis of C₅ --O--BF₂

Pentanol, 0.2 ml (1.84 mmole) was dissolved in 5 ml dichloromethane. Tothis solution, 20 ml of saturated solution of dichloromethane with BF₃was added at room temperature. This mixture was stirred for 15 minutes.Dichloromethane and residual BF₃ was removed under vacuum.

Polymerization of Isobutylene

The polymerization was carried out in a high vacuum apparatus as shownin FIG. 7. The system consists of two 100 ml flasks (10 and 20) and onestopcock (30) was used to separate flasks. The other stopcock (40) wasused to control the vacuum condition and nitrogen flow. In the dry box,the immobilized Lewis acid catalyst, such as 100 mg of catalyst (A), wascharged to the flask A, the valve (40) was then closed. The wholeapparatus was moved to a vacuum line and was pumped to high vacuumbefore closing the valve (40). Isobutylene (4 ml, 50 mmole) wascondensed in the flask B and dissolved in about 20 ml hexane which wasvacuum-distilled into the flask B. Isobutylene solution was warmed up torequired temperature and transferred to the catalyst in flask A. Afterstirring the reaction mixture for required time, PIB solution wasseparated from immobilized catalyst by filtration in the dry boxcondition. PIB was obtained by evaporating the solvent under vacuum. Theimmobilized catalyst was then recharged to the flask A and the entireprocess was repeated.

EXAMPLE 54 Polymerization of Isobutylene by Polyolefin ImmobilizedCatalysts

The polymer immobilized catalyst was used as the Lewis acid catalyst (A)in the carbocationic polymerization of isobutylene as follows: ##STR20##After the polymerization reaction, polymer solution (PIB) was filteredout and catalyst was reused in the subsequent polymerization reactions.In other words, the recovered catalyst was contacted with anotherisobutylene/hexane solution again, then following the same separationand recovery processes. The immobilized catalyst usually was recycledfor a number of times without any significant reduction in its activity.Table 6 summarizes the results of PIB prepared by the fine powder form(particle size<1 mm) of catalyst (A), polypropylene bounded --OAlCl₂catalyst.

                  TABLE 6                                                         ______________________________________                                        A Summary of PIB Prepared by PP-O--AlCl.sub.2 (fine powder)                                           Time              Yield                               Run # Solvent  Temp.    (Min) Mn    PDI   %                                   ______________________________________                                        1     hexane   RT       90    1,050 2.0   100                                 2     hexane   RT       60    1,150 1.6   100                                 3     hexane   RT       20    1,150 1.8   100                                 4     hexane   RT       15    1,140 1.6   100                                 8     hexane   RT       15    1,180 1.5   100                                 10    hexane   0° C.                                                                           15    4,540  2.57 100                                 *     hexane   RT       15    1,180 2.3   100                                 *     hexane   0° C.                                                                           15    5,450  2.63 100                                 ______________________________________                                         (* Control, pentanol based C.sub.5O--AlCl.sub.2 catalyst)                

The monomer to catalyst ratio was about 500. In most reaction cycles,the qualitative conversion from monomer to polymer was completed within15 minutes. The same reactivity can be maintained in subsequent reactioncycles. This high catalyst reactivity is very unusual, especially in theheterogeneous reaction. The polymer-immobilize catalyst almost had thesame activity as the corresponding small molecule, C₅ --O--AlCl₂, whichwas used as the control experiment and was studied under the samereaction condition.

EXAMPLE 55

Table 7 shows another result of PIB prepared by catalyst (A) with thesame overall catalyst concentration. However, catalyst (A) had particlesize>5 mm, instead of the fine powder form. The experimental results ofmany consecutive reaction cycles are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                        A Summary of PIB Prepared by PP-O--AlCl.sub.2 (chunk)                                                 Time              Yield                               Run # Solvent  Temp.    (Min) Mn    PDI   %                                   ______________________________________                                        1     hexane   RT       3     1,370 3.03  100                                 2     hexane   RT       2     1,660 2.59  100                                 3     hexane   RT       1     1,230 2.36   65                                 4     hexane   RT       3     1,110 2.56  100                                 8     hexane   RT       2     1,400 2.38   92                                 14    hexane   RT       3     1,320 2.57  100                                 15    hexane   0° C.                                                                           5     5,450 2.63   76                                 ______________________________________                                    

In this case, the yield of PIB is very dependent on the reaction time.It required about three hours to complete the conversion. This slowcarbocationic polymerization of isobutylene is believed to be due to theavailability of catalyst. The big particles of PP--O--AlCl₂ are believedto greatly reduce the surface area of catalyst. The number of the activesites on the surface was very small. Despite the difference in thereaction rate upon the particle size, the catalyst can be recovered andreused in the subsequent reaction cycles. Elemental analysis and ²⁷ AlNMR results show no significant change in the aluminum species aftermore than 10 reaction cycles.

EXAMPLE 56

In general, the use of the other immobilized catalysts, such as catalyst(B) and (C) as recited above, resulted in the same recycle and reuse ofthe catalysts as obtained in the isobutylene polymerization usingcatalyst (A). The same surface area-activity relationship was alsoobserved. However, the resulting PIB structures, in terms of molecularweight, molecular weight distribution and unsaturation, were quitedifferent. As shown in Examples 36-42, catalyst (B) resulted in highermolecular weight PIB than catalyst (A), and the molecular weightdistribution of PIB was usually very broad, even bimodal. Thisphenomenon may be related to the multiple reactive species, --OAlEtCland --O)₂ AlEt, involved in the polymerization.

On the other hand, the catalyst (C), PB--O--BF₂, produced, using thesame process as Examples 36-42, relatively low molecular weight PIB withquite narrow molecular weight distribution as shown in Table 8.

                  TABLE 8                                                         ______________________________________                                        A Summary of PIB Prepared by PB-O--BF.sub.3 (powder)                                                  Time              Yield                               Run # Solvent  Temp.    (Min) Mn    PDI   %                                   ______________________________________                                        1     hexane   RT       15    405   1.1   100                                 2     hexane   RT       15    450   1.2   100                                 3     hexane   RT       15    450   1.2   100                                 4     hexane   RT       15    420   1.4   100                                 5     hexane   0° C.                                                                           15    580   1.2   100                                 8     hexane   0° C.                                                                           15    640   1.5   100                                 *     hexane   RT        5    500   1.9   100                                 *     hexane   0° C.                                                                            5    1080  2.0   100                                 ______________________________________                                         (* Control, using pentanol based C.sub.5O--BF.sub.2 soluble catalyst)    

Molecular Structure of PIB

FIGS. 2 and 2A show the ¹ H NMR spectrum of PIB which was prepared bycatalyst (A) (PP--O--AlCl₂) at room temperature. The overall spectrum isvery similar to those of PIB prepared by soluble Al catalysts, such asAlCl₃, EtAlCl₂, Et₂ AlCl, and the controlling C₅ --O--AlCl₂ catalyst.Two major peaks are at 0.95 and 1.09 ppm, due to CH₃ and CH₂ protons inPIB polymer. There are some weak peaks located in the olefinic region,between 4.5 and 6.0 ppm.

The unsaturated double bond in polymer chain is the evidence of protonchain transfer reaction during the polymerization. In conjunction withthe GPC molecular weight studies, the integrative intensity of olefinicregion implies on average a double bond per polymer chain. In details,there are two quartets at 5.4 and 5.2 ppm and two singlets at 4.9 and4.6 ppm. The singlets at 4.9 and 4.6 ppm are indicative of two types ofnonequivalent vinylidene hydrogens, as recited in 25, which may belocated at the end of polymer chain. The quartets at 5.4 and 5.2 ppm arethe olefinic hydrogens coupled to methyl group, which are due to theinternal double bonds, as recited in 26. The ¹ H NMR peak assignmentsare summarized in Table I above.

A significantly high amount of internal double bonds with variousstructures are present, which indicates carbocationic isomerizationtaking place by Lewis acid catalyst after the polymerization reaction.

Reactive PIB

A different ¹ H NMR spectra of PIB was observed by using immobilizedcatalyst C (PB--O--BF₂) at 25 and 0° C. As shown in FIGS. 3 and 3A, thechemical shifts in double bond region consist of two major singlets at4.9 and 4.6 ppm, corresponding to terminal double bond, and two smallpeaks at 5.15 ppm, corresponding to internal double bond.

Comparing the integrated intensities between olefinic peaks, shown inFIG. 3A, the PIB prepared at 0° C. contains more than 85% of terminaldouble bonds. Theoretically, the maximum percentage of terminal doublebonds in the final PIB cannot be more than 75%. It is reasonable tospeculate that some effects from the substrate may play a role tocontrol the termination reactions and to avoid any isomerizationreactions. The control experiment, using C₅ --O--BF₂ soluble catalystunder the same reaction condition, resulted in more than 30 mole % ofinternal double bonds.

Although this invention has been shown and described with respect to thedetailed embodiments thereof, it will be understood by those skilled inthe art that various changes in form and detail thereof may be madewithout departing from the spirit and scope of the claimed invention.

We claim:
 1. A process for alkylating a substrate selected from thegroup consisting of olefin, alkane, alkyl halide, aromatic compound, andhydroxy aromatic compound with an alkylating agent selected from atleast one member of the group consisting of olefin, alkane, and alkylhalide which comprises contacting a mixture of substrate and alkylatingagent in the presence of immobilized Lewis Acid catalyst in a manner andunder conditions sufficient to alkylate the substrate with thealkylating agent subject to the proviso that the alkylating agent isselected to be different from the substrate employed; and wherein theimmobilized catalyst comprises polymer having at least one Lewis Acidimmobilized within the structure therein, said polymer having monomerunits represented by the structural formula:

    --[A].sub.a --[B].sub.b --[C].sub.c --

wherein a represents about 1 to about 99 mole % b represents about 0 toabout 50 mole % c represents about 1 to about 99 mole % a+b+c ispreferably about 100%; ##STR21## C is selected from the group consistingof: ##STR22## (III) combinations thereof, wherein D is OH, halide, OR⁴,NH₂, NHR³, OM', or OM"; E is the residue of the reaction of at least oneLewis Acid with the D substituent of monomer unit B; R¹ representsproton, C₁ -C₂₄ alkyl group, or C₃ -C₂₄ cycloalkyl; R² represents C₁-C₂₄ alkylene group, C₃ -C₂₄ cycloalkylene, C₆ -C₁₈ arylene, or C₇ -C₃₀alkylarylene; R³ represents C₁ -C₂₄ alkyl, C₃ -C₂₄ cycloalkyl, Cl--C₂₄aryl, or C₇ -C₃₀ alkylaryl; R⁴ represents C₁ -C₂₄ alkyl, C₃ -C₂₄cycloalkyl, C₁ -C₂₄ aryl, or C₇ -C₃₀ alkylaryl; M' represents alkalimetal; and M" represents alkaline-earth metal, wherein said immobilizedcatalyst is derived from a functionalized copolymer having a numberaverage molecular weight of from 3,000 to 10,000,000 and having thestructural formula ##STR23## wherein A, B and a are defined above and drepresents about 1 to about 99 mole %, and being equal to the sum ofb+c.
 2. The process of claim 1 wherein in the immobilized catalyst,substituent E is derived from Lewis Acid selected from the groupconsisting of boron halides, aluminum halides, alkyl aluminum halides,titanium halides, titanium halides and combinations thereof.
 3. Theprocess of claim 1 wherein in the immobilized catalyst monomer unit A isderived from propylene, 1-butene, ethylene and mixtures thereof.
 4. Theprocess of claim 1 wherein in the immobilized catalyst monomer unit A isderived from propylene.
 5. The process of claim 1 wherein in theimmobilized catalyst monomer unit A is derived from 1-butene.
 6. Theprocess of claim 1 wherein [C] is: ##STR24##
 7. The process of claim 6wherein in said immoblized catalyst, R² is C₃ to C₂₀ alkylene.
 8. Theprocess of claim 1 wherein the value of a is at least about 50 mole %.9. The process of claim 1 wherein an aromatic compound is alkylated. 10.The process of claim 1 wherein a hydroxyaromatic compound is alkylated.11. The process of any one of claims 9 and 10 wherein the alkylatingagent is an alkane.
 12. The process of any one of claims 9 and 10wherein the alkylating agent is an an olefin.
 13. The process of any oneof claims 9 and 10 wherein the alkylating agent is alkyl halide.
 14. Theprocess of claim 1 wherein b is substantially 0 mole %.
 15. The processof claim 1 wherein R² is a C₃ to C₅ alkylene group.
 16. The process ofclaim 1 wherein said immobilized catalyst is a solid.
 17. The process ofclaim 16 wherein said immobilized catalyst has a particle sizedistribution of from about 0.001 to about 1.0 mm.
 18. The process ofclaim 17 wherein said particle size distribution is from about 0.01 toabout 0.5 mm.